US20100056421A1 - Fabric care compositions, process of making, and method of use - Google Patents

Fabric care compositions, process of making, and method of use Download PDF

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Publication number
US20100056421A1
US20100056421A1 US12/549,413 US54941309A US2010056421A1 US 20100056421 A1 US20100056421 A1 US 20100056421A1 US 54941309 A US54941309 A US 54941309A US 2010056421 A1 US2010056421 A1 US 2010056421A1
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Prior art keywords
poly
process according
polymer
surfactant
acrylamide
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US12/549,413
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US8372795B2 (en
Inventor
Alessandro Corona, III
Gayle Marie Frankenbach
Seth Edward Lindberg
Mark Robert Sivik
Patrick Thomas Spicer
Gregory Thomas Waning
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to US12/549,413 priority Critical patent/US8372795B2/en
Assigned to THE PROCTER & GAMBLE COMPANY reassignment THE PROCTER & GAMBLE COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SIVIK, MARK ROBERT, SPICER, PATRICK THOMAS, FRANKENBACH, GAYLE MARIE, LINDBERG, SETH EDWARD, CORONA, ALESSANDRO NMN, III, WANING, GREGORY THOMAS
Priority to BRPI0924622A priority patent/BRPI0924622A2/en
Priority to PCT/US2009/061424 priority patent/WO2011002475A1/en
Priority to CA2764101A priority patent/CA2764101A1/en
Priority to EP09744010A priority patent/EP2449077A1/en
Priority to MX2011013918A priority patent/MX2011013918A/en
Publication of US20100056421A1 publication Critical patent/US20100056421A1/en
Publication of US8372795B2 publication Critical patent/US8372795B2/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam
    • C11D2111/44
    • C11D2111/46

Definitions

  • compositions comprising a cationic polymer and anionic surfactant are disclosed.
  • a process of making stable compositions comprising cationic polymer and anionic surfactant are disclosed.
  • cationic polymers and anionic surfactants may provide certain benefits to a fabric or other substrate, due to the opposing charges, such agents may be difficult to formulate, particularly when higher levels of such materials are used.
  • cationic polymers tend to agglomerate with anionic surfactants, such as those typically used in detergent compositions, to create an unpourable, phase-separated mixture, which is generally not compatible with consumer use.
  • the instant disclosure relates to care and/or cleaning compositions capable of providing one or more benefits to a fabric, particularly a color care benefit, and methods for providing same.
  • the term “comprising” means various components conjointly employed in the preparation of the compositions of the present disclosure. Accordingly, the terms “consisting essentially of” and “consisting of” are embodied in the term “comprising”.
  • additive means a composition or material that may be used separately from (but including before, after, or simultaneously with) the detergent during a laundering process to impart a benefit to the treated fabric.
  • charge density refers to the charge density of the polymer itself and may be different from the monomer feedstock. Charge density may be calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit. The positive charges may be located on the backbone of the polymers and/or the side chains of polymers. For polymers with amine monomers, the charge density depends on the pH of the carrier. For these polymers, charge density is measured at a pH of 7.
  • coacervate means a particle formed from the association of a cationic polymer and an anionic surfactant in an aqueous environment.
  • the term “coacervate” may be used interchangeably with the terms “primary particle,” “colloidal particle,” and “aggregate particle.”
  • colloidal particles means an aggregate of primary particles.
  • essentially free of a component means that no amount of that component is deliberately incorporated into the composition.
  • the term “external structurant” refers to a selected compound or mixture of compounds which provides structure to a detergent composition independently from, or extrinsic from, any structuring effect of the detersive surfactants present in the composition.
  • compositions include fabric care compositions for handwash, machine wash and/or other purposes and include fabric care additive compositions and compositions suitable for use in the soaking and/or pretreatment of fabrics. They may take the form of, for example, laundry detergents, fabric conditioners and/or other wash, rinse, dryer added products, and sprays. Compositions in the liquid form may be in an aqueous carrier. In other aspects, the fabric care compositions are in the form of a granular detergent or dryer added fabric softener sheet.
  • the term includes, unless otherwise indicated, granular or powder-form all-purpose or “heavy-duty” washing agents, especially cleaning detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called heavy-duty liquid types; liquid fine-fabric detergents; cleaning auxiliaries such as bleach additives and “stain-stick” or pre-treat types, substrate-laden products, dry and wetted wipes and pads, nonwoven substrates, and sponges; and sprays and mists.
  • Various dosage formats may be used.
  • the composition may be provided in pouches, including foil or plastic pouches or water soluble pouches, such as a polyvinyl alcohol (PVA) pouch; dosing balls or containers; containers with readily opened closures, such as pull tabs, screw caps, foil or plastic covers, and the like; or other container known in the art.
  • the compositions may be compact compositions, comprising less than about 15%, or less than about 10%, or less than about 7% water.
  • High charge density means a charge density of greater than about 1 meq/g.
  • Low charge density means a charge density of less than about 1 meq/g.
  • the phrase “high molecular weight” means a molecular weight of greater than about 1,000,000 kD.
  • isotropic means a clear mixture, (having no visible haziness and/or dispersed particles) and having a uniform transparent appearance.
  • structured phase means that portion of a composition comprising primary and/or colloidal particles when separated by centrifugation.
  • continuous phase means that portion of a composition substantially free from particles upon separation by centrifugation.
  • stable means that no visible phase separation is observed for a period of at least about two weeks, or at least about four weeks, or greater than about a month or greater than about four months, as measured using the Floc Formation Test, described in USPA 2008/0263780 A1.
  • unit dose means an amount of fabric care composition suitable to treat one load of laundry, such as from about 0.05 to about 100 g, or from 10 to about 60 g, or from about 20 to about 40 g.
  • test methods disclosed in the present application should be used to determine the respective values of the parameters of Applicants' invention.
  • component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • the cationic polymers of the disclosed compositions are useful for providing one or more fabric benefits, such as a color rejuvenation benefit, as a result of cationic polymer coalescence with anionic surfactant to form a coacervate system.
  • This is believed to deliver a benefit to the treated fabric without the necessity of dyes or other coloring agents via formation of a thin film on the fiber of the treated fabric.
  • the direct combination for example via simple mixing, of anionic surfactant and cationic polymers yields an unstable solution, wherein the surfactant and polymers aggregate to form an unstable composition with a rheology unsuitable for consumer use.
  • Applicants have recognized that, by separating a mixture of cationic polymer and a mixture of anionic surfactant, and combining via a high energy milling step, surfactant-polymer particles of a certain size can be formed. Without being bound by theory, by forming particles of the dimensions disclosed herein, a stable, homogeneous solution containing cationic polymer and anionic surfactant can be achieved.
  • a process for preparing a composition comprising a structured phase and optionally, a continuous phase, is disclosed, wherein said process comprises the steps of
  • the dispersion energies of steps (a) and (b) can be characterized as having a certain Energy Density, wherein Energy Density is generated by exerting a power density on the feed within the mixing chamber for a residence time.
  • Residence time means the average amount of time a fluid remains within the mixing chamber and is determined by calculating the active volume of the device where the fluid stream receives the highest concentration of power input divided by the flow rate of the stream out of the mixing chamber.
  • the high energy dispersion step can be also be characterized by power density and residence time.
  • the energy level of the high energy dispersion step may be empirically determined by one of skill in the art, by analysis of the particle size and distribution of the second mixture and subsequent adjustment of the mixing energy applied when generating the mixture, provided the energy level is sufficient to achieve the primary particle size and distribution as described.
  • the disclosed processes use relatively high power density to achieve the desired colloid attributes.
  • mixing power densities are in the range of 1 W/ml to 1000 W/ml.
  • power density ranges from about 1000 W/ml to about 100,000 W/ml (See “A Physical Interpretation of Drop Sizes in Homogenizers and Agitated Tanks, Including the Dispersion of Viscous Oils,” J. T. Davies, Chemical Engineering Science, Vol. 42, No 7, pp 1671-1676, 1987.
  • the energy level may be applied in an amount sufficient to achieve the primary particle size and distribution disclosed herein.
  • the high energy dispersion step may have an Energy Density of from about 0.1 to about 100 J/ml, or from about 0.5 to about 50 J/ml, or from about 1 to about 10 J/ml.
  • the energy density may be generated from a power density of from about 0.01 to about 1,000,000 W/ml, or from about 0.1 to about 100,000 W/ml.
  • the residence time may be from about 1 millisecond to about 10 seconds, or from about 1 millisecond to about 1 second, or from about 2 milliseconds to about 100 milliseconds.
  • the residence time may be less than 10 seconds and the power density may be greater than about 0.01 W/ml. In one aspect, the residence time may be less than 1 second and the power density may be greater than about 0.1 W/ml. In one aspect, the residence time may be less than 100 milliseconds and the power density may be greater than about 1 W/ml.
  • metered streams of the polymer mixture and surfactant mixture may be combined continuously in a pipe where the fluids are intimately contacted with each other in one or more high shear mechanical or static mixers.
  • Mechanical mixers include rotor stator mills (e.g. manufactured by IKA, Silverson, Quadro-Ytron), colloid mills (IKA, Premier), Stirred Bead Mills (Romaco)).
  • Static mixers may consist of an array of similar, stationary mixing elements, placed one behind the other in a pipe or channel (eg. manufactured for instance by Sulzer Ltd., Koch-Glitsch Inc., and Chemineer Inc).
  • Static mixers suitable for this process also include orifice, microchannel or valve-type mixers.
  • the polymer mixture may be contacted with the surfactant mixture in an agitated batch making tank to form the premix.
  • the polymer mixture may be injected into the high shear region of a high shear blender (e.g. IKA T-series batch high shear mixers).
  • the mixing device energy may be any device, provided that sufficient energy is provided to create colloid particles of the desired composition, unit particle size, and particle birefringent optical characteristics.
  • Fine mixing of the polymer mixture with the surfactant mixture results in the formation of primary particles having a primary particle size distribution as described above dispersed in the third mixture, or “premix.” Any larger than desired particles formed during blending can also be reduced in size by additional high shear milling steps.
  • the premix can then be used for subsequent formulation as either a detergent, additive, rinse-added solution, or the like.
  • the structurant may be incorporated into the third solution/premix with a low energy dispersion step sufficient to achieve adequate incorporation of structuring agents to aid in suspension of the colloid particles in the composition.
  • Incorporation mixing processes can be in the form of continuous static mixers or batch tank agitation where power densities range from about 0.0001 W/ml to about 10 W/ml.
  • mechanical high shear mixers and constricted flow type (e.g. orifices) mixers with power densities of from about 1 W/ml to about 1000 W/ml can be used.
  • the low energy dispersion of step (b) has an energy density from about 0.001 to about 1 J/ml, or from about 0.1 to about 10 J/ml, or from about 0.005 to about 0.5 J/ml.
  • the energy density is generated from a power density of from about 0.0001 W/ml to about 10 W/ml, alternatively from about 1 W/ml to about 1000 W/ml.
  • the low energy dispersion of step (b) may comprise an energy density generated from a power density of from about 0.01 to about 1,000,000 W/ml, or from about 0.1 to about 100,000 W/ml wherein the residence time may be from about 1 millisecond to about 10 seconds, or from about 1 millisecond to about 1 sec, or from about 2 milliseconds to about 100 ms.
  • the residence time when the residence time is less than 10 seconds, the power density may be greater than about 0.01 W/ml.
  • the residence time is less than 1 second, the power density may be greater than about 0.1 W/ml.
  • the residence time is less than 100 milliseconds, the power density may be greater than about 1 W/ml.
  • the energy input from the mixing device may be lowered so as to prevent damage to the structurant. Entrainment of air may be limited throughout the process.
  • the particles may comprise primary particles having a primary particle size of from about 0.05 to about 500 ⁇ m, or from about 0.1 to about 250 ⁇ m, or from about 0.5 to about 50 ⁇ m. In one aspect, from about 70% to about 100%, based on total number of primary particles, of the primary particles have a particle size within this range. In one aspect, the high energy dispersion step may form primary particles having a primary particle size distribution such that at least 70% of the primary particles, based on total number of primary particles, have a particle size of less than about 50 ⁇ m.
  • the particles may comprise colloidal particles, wherein the colloidal particles have a colloidal particle size from about 0.05 to about 1000 ⁇ m, or from about 0.5 to about 500 ⁇ m, or from about 1.0 to about 50 ⁇ m. In one aspect, from about 70% to about 100% of the colloidal particles, based on total number of colloidal particles, have a particle size within this range. In one aspect, the high energy dispersion step may form colloidal particles having a colloidal particle size distribution such that at least 70% of the colloidal particles, based on total number of colloidal particles, have a particle size of less than about 500 ⁇ m.
  • the cationic polymer may comprise a cationic polymer produced by polymerization of ethylenically unsaturated monomers using a suitable initiator or catalyst. These are disclosed in WO 00/56849 and U.S. Pat. No. 6,642,200.
  • the cationic polymer may be selected from the group consisting of cationic or amphoteric polysaccharides, polyethyleneimine and its derivatives, a synthetic polymer made by polymerizing one or more cationic monomers selected from the group consisting of N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl methacrylate, N,N-dialkylaminoalkyl acrylamide, N,N-dialkylaminoalkylmethacrylamide, quaternized N,N dialkylaminoalkyl acrylate quaternized N,N-dialkylaminoalkyl methacrylate, quaternized N,N-dialkylaminoalkyl acrylamide, quaternized N,N-dialkylaminoalkylmethacrylamide, Methacryloamidopropylpentamethyl-1,3-propylene-2-ol-ammonium dichloride, N,N,N,N′,
  • the cationic polymer may optionally comprise a second monomer selected from the group consisting of acrylamide, N,N-dialkyl acrylamide, methacrylamide, N,N-dialkylmethacrylamide, C 1 -C 12 alkyl acrylate, C 1 -C 12 hydroxyalkyl acrylate, polyalkylene glyol acrylate, C 1 -C 12 alkyl methacrylate, C 1 -C 12 hydroxyalkyl methacrylate, polyalkylene glycol methacrylate, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl caprolactam, and derivatives, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethane sulfonic acid (AMPS) and their salts.
  • the polymer may be a terpolymer made from more than two monomers.
  • the polymer may optionally be branched or cross-linked by using branching and crosslinking monomers.
  • Branching and crosslinking monomers include ethylene glycoldiacrylate divinylbenzene, and butadiene.
  • the cationic polymer may include those produced by polymerization of ethylenically unsaturated monomers using a suitable initiator or catalyst, such as those disclosed in WO 00/56849 and U.S. Pat. No. 6,642,200.
  • the cationic polymer may comprise charge neutralizing anions such that the overall polymer is neutral under ambient conditions.
  • Suitable counter ions include (in addition to anionic species generated during use) include chloride, bromide, sulfate, methylsulfate, sulfonate, methylsulfonate, carbonate, bicarbonate, formate, acetate, citrate, nitrate, and mixtures thereof.
  • the cationic polymer may be selected from the group consisting of poly(acrylamide-co-diallyldimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate) and its quaternized derivative, poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride-co-acryl
  • cationic polymers include and may be further described by the nomenclature Polyquaternium-1, Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-8, Polyquaternium-1, Polyquaternium-14, Polyquaternium-22, Polyquaternium-28, Polyquaternium-30, Polyquaternium-32 and Polyquaternium-33, as named under the International Nomenclature for Cosmetic Ingredients.
  • the cationic polymer may comprise a cationic acrylic based polymer. In one aspect, the cationic polymer may comprise a cationic polyacrylamide. In one aspect, the cationic polymer may comprise poly(acrylamide-N,N-dimethylaminoethyl acrylate) and its quaternized derivatives. In this aspect, the cationic polymer may be that sold under the tradename Sedipur®, available from BTC Specialty Chemicals, BASF Group, Florham Park, N.J.
  • the cationic polymer may comprise poly(acrylamide-co-methacrylamidopropyltrimethyl ammonium chloride).
  • the cationic polymer may comprise a non-acrylamide based polymer, such as that sold under the tradename Rheovis® CDE, available from Ciba Specialty Chemicals, a BASF group, Florham Park, N.J., or as disclosed in USPA 2006/0252668.
  • a non-acrylamide based polymer such as that sold under the tradename Rheovis® CDE, available from Ciba Specialty Chemicals, a BASF group, Florham Park, N.J., or as disclosed in USPA 2006/0252668.
  • the cationic polymer may comprise polyethyleneimine or a polyethyleneimine derivative.
  • the cationic polymer may be a polyethyleneinine such as that sold under the tradename Lupasol® by BASF, AG, Lugwigschaefen, Germany
  • the cationic polymer may include alkylamine-epichlorohydrin polymers, which are reaction products of amines and oligoamines with epicholorohydrin. These include those polymers listed in U.S. Pat. Nos. 6,642,200 and 6,551,986. Examples include dimethylamine-epichlorohydrin-ethylenediamine, and available under the trade name Cartafix® CB and Cartafix® TSF from Clariant, Basle, Switzerland.
  • the cationic polymer may comprise a synthetic cationic polymer comprising polyamidoamine-epichlorohydrin (PAE) resins of polyalkylenepolyamine with polycarboxylic acid.
  • PAE resins are the condensation products of diethylenetriamine with adipic acid followed by a subsequent reaction with epichlorohydrin. They are available from Hercules Inc. of Wilmington Del. under the trade name KymeneTM or from BASF AG (Ludwigshafen, Germany) under the trade name LuresinTM. These polymers are described in Wet Strength resins and their applications edited by L. L. Chan, TAPPI Press (1994), at pp. 13-44.
  • the cationic polymer may be selected from the group consisting of cationic or amphoteric polysaccharides.
  • the cationic polymer may comprise a polymer selected from the group consisting of cationic and amphoteric cellulose ethers, cationic or amphoteric galactomanan, cationic guar gum, cationic or amphoteric starch, and combinations thereof.
  • the cationic polymer may comprise an amphoteric polymer, provided the polymer possesses a net positive charge.
  • Said polymer may have a cationic charge density of about 0.05 to about 18 milliequivalents/g.
  • the cationic polymer may have a cationic charge density of from about 0.005 to about 23 milliequivalents/g, from about 0.01 to about 12 milliequivalents/g, or from about 0.1 to about 7 milliequivalents/g, at the pH of the intended use of the composition.
  • charge density is measured at the intended use pH of the product. Such pH will generally range from about 2 to about 11, more generally from about 2.5 to about 9.5.
  • Charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit.
  • the positive charges may be located on the backbone of the polymers and/or the side chains of polymers.
  • the cationic polymer may have a weight-average molecular weight of from about 500 to about 5,000,000 Daltons, or from about 1,000 to about 2,000,000 Daltons, or from about 2,500 to about 1,500,000 Daltons as determined by size exclusion chromatography relative to polyethyleneoxide standards with RI detection.
  • the molecular weight of the cationic polymer may be from about 500 to about 37,500 kD.
  • the cationic polymers may also range in both molecular weight and charge density.
  • the cationic polymer may have a charge density of from about 0.05 to about 12 meq/g, or from about 1.0 to about 6 meq/q, or from about 3 to about 4 meq/g at a pH of from about 3 to about 9.
  • the one or more cationic polymer may have a weight-average molecular weight of 500 to about 37,500 Daltons and a charge density of from about 0.1 meq/g to about 12.
  • the polymer mixture may have a viscosity of from about 1 to about 1,000, or from about 400 to about 800 cps at 20/s.
  • the polymer mixture may optionally include a surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, and combinations thereof.
  • a surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, and combinations thereof.
  • the polymer mixture may be isotropic.
  • the polymer mixture may comprise a structurant.
  • the surfactant mixture may comprise anionic surfactant.
  • suitable anionic surfactants include those described in USPA 12/075333.
  • the HLB value of the anionic surfactant may be from about 4 to about 14, or from about 8 to about 10, or about 9.
  • the surfactant The surfactant mixture may be provided in the form of a solution comprising, based on total weight of the surfactant mixture, from about 10% to about 70% of a solvent.
  • the solvent may comprise a low molecular weight water-miscible molecule.
  • the solvent may be water.
  • the surfactant mixture may have a viscosity of from about 1 to about 1,000 cps at 20/s, or from about 400 to about 800 cps at 20/s, or about 400 cps at 20/s.
  • the surfactant mixture may have a pH of about 7.0.
  • the pH may be adjusted, using any suitable pH adjusting agent.
  • the surfactant mixture may be isotropic.
  • the surfactant mixture may comprise a structurant.
  • the polymer and surfactant mixtures may be prepared by means familiar to those in the art.
  • the polymer mixture and/or surfactant mixture can optionally include one or more adjunct ingredients as described herein.
  • the composition may comprise, based on total weight of the composition, from about 0.1% to about 30%, or from about 0.5% to about 20%, or from about 1.0% to about 10%, or from about 1.5% to about 8%, of a cationic polymer.
  • the composition may comprise, based on total weight of the composition, of from about 2% to about 50%, or from about 5% to about 25%, or from about 12% to about 20% of an anionic surfactant.
  • the anionic surfactant may comprise a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, zwitterionic surfactants, and combinations thereof.
  • the composition may comprise, based on total weight of the composition, from about 1.0% to about 50%, or from about 7% to about 40%, or from about 10% to about 20% of alkylethoxysulfonate (AES). In one aspect, the composition may comprise, based on total weight of the composition, less than about 5%, or less than about 10%, or less than about 50% HLAS.
  • AES alkylethoxysulfonate
  • the composition may comprise, based on total weight of the composition, from about 0.001% to 1.0%, or from 0.05% to 0.5%, or from 0.1% to 0.3% of an external structurant.
  • Suitable structurants include those described, for example, in USPAs 2007/169741B2 and 2005/0203213.
  • the structurant may comprise hydrogenated castor oil, commercially available as under the trade name Thixin®.
  • the composition may have a resting (low shear) viscosity of greater than about 10,000 cps@0.05/s.
  • the low shear viscosity may be from about 10,000 to about 225,000 cps@0.05/s, or from about 30,000 to about 100,000 cps@0.05/s, or from about 10,000 to about 50,000 cps@0.05/s.
  • the composition may comprise a dispersing agent.
  • the composition may comprise, based on total weight of the composition, from about 0% to about 7%, or from about 0.1% to about 5%, or from about 0.2% to about 3% of a dispersing agent.
  • the dispersing agent may be substantially water soluble.
  • the dispersing agent may be present in the surfactant mixture, the polymer mixture, the premix, the final composition, or a combination thereof.
  • the dispersing agent may be a nonionic surfactant.
  • Suitable nonionic surfactants include addition products of ethylene oxide and, optionally, propylene oxide, with fatty alcohols, fatty acids, fatty amines, etc. They may be referred to herein as ethoxylated fatty alcohols, ethoxylated fatty acids, and ethoxylated fatty amines. Any of the ethoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant.
  • Suitable compounds include surfactants of the general formula: R 1 —Y—(C 2 H 4 O) Z —C 2 H 4 OH wherein R 1 may be selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups, and primary, secondary and branched chain alkyl- and alkenyl substituted phenolic hydrocarbyl groups; said hydrocarbyl groups having a hydrocarbyl chain length of from about 8 to about 20, or from about 9 to about 18 carbon atoms.
  • Y may be —O—, —C(O)O—, or —O—, and in which R 1 , when present, have the meanings given hereinbefore, and z may be at least about 4, or about 7 to about 25.
  • the dispersing agent may include a material having the general formula: R 1 O(CH(R 2 )CH 2 O)x(CH 2 CH 2 O)yR 3 or R 1 O(CH 2 CH 2 O)x(CH(R 2 )CH 2 O)yR 3 wherein R 1 may be defined as above; R 2 may be a C 1 -C 3 alkyl unit; R 3 may be hydrogen or C 1 -C 3 alkyl, wherein x is from 1 to 100, and wherein y is from 0 to 20.
  • the individual alkoxy monomers may be arranged blockwise or randomly. Non-limiting examples include the Plurafac® surfactants from BASF.
  • Suitable dispersing agents include the so-called propyleneoxide/ethyleneoxide block copolymers, having the following general structure: HO(CH 2 CH2O)x(CH(CH 3 )CH 2 O)y (CH 2 CH 2 O)zH, wherein x is from 1 to 100, wherein y is from 0 to 20, and z is from 0 to 100.
  • Such agents include the Pluronic® PE compounds available from BASF.
  • Adjunct ingredient may comprise a material selected from the group consisting of fatty acids, brighteners, chelating agents, dye transfer inhibiting agents, enzymes, enzyme stabilizers, and pearlescent agents.
  • Such adjuncts may be suitable for use in the instant compositions and may be desirably incorporated in certain aspects. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use may be found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.
  • the adjunct ingredients may be provided in the surfactant mixture, the polymer mixture, the premix, the final composition, or any combination thereof.
  • compositions made according to the disclosed methods as compared to compositions made via simple mixing are set forth in Table 1.
  • Composition Stability Composition Process Used Phase Stability 3% Merquat 100, 17% AES (anionic High energy Stable for 4 surfactant) using water as a carrier dispersion months 3% Merquat 100, 17% AES (anionic Simple mixing Phase split surfactant) using water as a carrier after 2 days
  • Particle sizing—Particle size and structure in neat product is determined via light microscopy.
  • a drop of neat product is placed on a glass microscope slide and covered with a glass coverslip.
  • the coacervate particles are identified by their birefringent nature indicating a liquid crystalline character. These coacervate particles can be identified from other possible particulates in the formulation both by this birefringent nature, and either by inspection of the formulation in the absence of cationic polymer, and hence, in the absence of coacervate formation, or by systematic evaluation of other components in the mixture. Quantification of primary and colloidal particle size is completed by image analysis of the microscopy pictures.
  • enhanced contrast techniques are used to improve contrast between the coacervate particles and the surrounding liquid, including differential interference contrast, phase contrast, polarized light, and/or the use of fluorescent dyes. Additional droplets are imaged to ensure that the resulting images and particle sizes are representative of the entire mixture.
  • Particle size under dilution may be determined using microscopy (light microscopy as described above, or electron microscopy if the particles are too small to be visible by light microscopy) and/or laser scattering techniques such as laser diffraction with Mie theory, dynamic light scattering, or focused beam reflectance mode. Often these techniques are used together, in that microscopy is used to identify the coacervate particles from other possible particulates in solution and scattering techniques offer a more rapid quantification of particle size.
  • the choice of scattering method depends on the particle size of interest and the concentration level of particles in solution.
  • DLS dynamic light scattering
  • the fluctuations in scattered light due to Brownian motion of the particles are measured. These fluctuations are correlated to obtain a diffusion coefficient and therefore a hydrodynamic radius of particles.
  • This technique is used when the particles are less than a few microns and the solution conditions are dilute.
  • laser diffraction the light scattered by the particles is measured by a series of detectors placed at different angles.
  • the use of back scattering detectors and Mie theory enables detection of particle sizes less than 1 micron.
  • This technique can be utilized to measure particles over a broader size range compared to DLS, and resolution of two populations of particle sizes (such as primary and colloidal particles) can be determined provided the difference in sizes is significant enough.
  • FBRM focused beam reflectance measurement
  • a chord length distribution which is a “fingerprint” of the particle size distribution, is obtained.
  • FBRM FBRM
  • a focused laser beam scans across particles in a circular path, and as the beam scans across particles the backscattered light is detected as pulses of light.
  • the duration of the pulse is converted to a chord length, and by measuring thousands of chord lengths each second, the chord length distribution is generated.
  • detection of two size populations can be obtained provided the differences in size is great enough. This technique is used when the particles are greater than approximately 1 micron and is particularly useful when the turbidity and/or particle concentration in solution is high.
  • the base composition is made by adding the component materials of Table 3 into a dish bottom tank. The component materials are mixed by hand to minimize the amount of air entrapped in the mixture. Upon complete blending, the resulting base composition is clear and isotropic, having a viscosity of from about 200 to about 800 cPS at 20 s ⁇ 1. 71 liters of base composition is then combined with 25 liters of the isotropic polymer solution. To form the polymer solution, the neat polymer (Nalco, Merquat 100, Homopolymer of diallyldimethyl ammonium chloride, polymer molecular weight of from about 100,000 to about 150,000, 40% active) is diluted with water to form an 11.9% active polymer solution.
  • the base composition is delivered at a rate of 3500 g/min using a Waukesha Pump Model (00602) and the polymer solution is delivered at a rate of 1265 g/min using a Pump (Moyno, E4ASSF3-SKA).
  • the polymer solution and base composition are delivered simultaneously to the head of mill (IKA DR2000/5, two fine grindsets, 50% energy setting).
  • the polymer solution is delivered via a dip tube inserted into the tubing such that the polymer solution is delivered as close as possible to the top of the grind sets without touching, thereby eliminating any air gap between the polymer introduction and dispersion with the base composition.
  • a mixture containing colloidal particles is formed.
  • Successful attainment of the colloidal particles can be confirmed at this step wherein a dispersed phase of colloid particles suspended in the product is visible via microscopy, the colloidal particles having a diameter of from about 10 to 20 um. Successful attainment of the colloidal particles can also be verified via observation of visible regions of birefringence in the dispersed phase using cross Polared microscopy.
  • Base Composition Formulation Base Composition Component Material (wt %) C25 AE1.8S surfactant 1 17.736% Sodium Hydroxide 2 2.513% Monoethanol Amine 3 2.217% 1,2 Propanediol 4 3.236% Diethylene Glycol 5 1.419% DTPA (diethylene triamine penta acetate) 6 0.443% Citric Acid 7 2.956% Sodium Cumene sulfate 8 1.552% C12-C18 Fatty Acid 9 1.848% Ethoxylated tetraethylene pentaimine 10 0.517% Ethanol 11 2.483% Perfume 0.61% N4 Amine (N,N′-Bis(3- 0.04% aminopropyl)ethylenediamine) 12 Merquat 100 13 25.316% Thixcin ® (organic derivative of castor oil) 14 0.15% Water to 100% 1 Available from The Procter & Gamble Company.

Abstract

The instant disclosure relates to processes for making stable compositions via combining a mixture containing at least one cationic polymer and a mixture containing at least one anionic surfactant in the presence of a high energy dispersion step, followed by incorporation of an external structurant using a low energy dispersion step, and compositions made according to the disclosed processes.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Ser. No. 61/092,633 filed Aug. 28, 2008, and U.S. Provisional Application Ser. No. 61/221,632 filed Jun. 30, 2009.
  • FIELD OF THE INVENTION
  • Compositions comprising a cationic polymer and anionic surfactant are disclosed. In one aspect, a process of making stable compositions comprising cationic polymer and anionic surfactant are disclosed.
  • BACKGROUND OF THE INVENTION
  • While combinations of cationic polymers and anionic surfactants may provide certain benefits to a fabric or other substrate, due to the opposing charges, such agents may be difficult to formulate, particularly when higher levels of such materials are used. At higher levels, cationic polymers tend to agglomerate with anionic surfactants, such as those typically used in detergent compositions, to create an unpourable, phase-separated mixture, which is generally not compatible with consumer use.
  • Accordingly, there is a need for processes that can provide a product containing cationic polymer and anionic surfactant, but which is sufficiently stable and has a rheology profile acceptable to consumers.
  • SUMMARY OF THE INVENTION
  • The instant disclosure relates to care and/or cleaning compositions capable of providing one or more benefits to a fabric, particularly a color care benefit, and methods for providing same.
  • DETAILED DESCRIPTION OF THE INVENTION
  • As used herein, the articles “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.
  • As used herein, the term “comprising” means various components conjointly employed in the preparation of the compositions of the present disclosure. Accordingly, the terms “consisting essentially of” and “consisting of” are embodied in the term “comprising”.
  • As used herein, the term “additive” means a composition or material that may be used separately from (but including before, after, or simultaneously with) the detergent during a laundering process to impart a benefit to the treated fabric.
  • As used herein, “charge density” refers to the charge density of the polymer itself and may be different from the monomer feedstock. Charge density may be calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit. The positive charges may be located on the backbone of the polymers and/or the side chains of polymers. For polymers with amine monomers, the charge density depends on the pH of the carrier. For these polymers, charge density is measured at a pH of 7.
  • As used herein, the term “coacervate” means a particle formed from the association of a cationic polymer and an anionic surfactant in an aqueous environment. The term “coacervate” may be used interchangeably with the terms “primary particle,” “colloidal particle,” and “aggregate particle.”
  • As used herein, the term “colloidal particles” means an aggregate of primary particles.
  • As defined herein, “essentially free of” a component means that no amount of that component is deliberately incorporated into the composition.
  • As used herein, the term “external structurant” refers to a selected compound or mixture of compounds which provides structure to a detergent composition independently from, or extrinsic from, any structuring effect of the detersive surfactants present in the composition.
  • As used herein, “compositions” include fabric care compositions for handwash, machine wash and/or other purposes and include fabric care additive compositions and compositions suitable for use in the soaking and/or pretreatment of fabrics. They may take the form of, for example, laundry detergents, fabric conditioners and/or other wash, rinse, dryer added products, and sprays. Compositions in the liquid form may be in an aqueous carrier. In other aspects, the fabric care compositions are in the form of a granular detergent or dryer added fabric softener sheet. The term includes, unless otherwise indicated, granular or powder-form all-purpose or “heavy-duty” washing agents, especially cleaning detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called heavy-duty liquid types; liquid fine-fabric detergents; cleaning auxiliaries such as bleach additives and “stain-stick” or pre-treat types, substrate-laden products, dry and wetted wipes and pads, nonwoven substrates, and sponges; and sprays and mists. Various dosage formats may be used. The composition may be provided in pouches, including foil or plastic pouches or water soluble pouches, such as a polyvinyl alcohol (PVA) pouch; dosing balls or containers; containers with readily opened closures, such as pull tabs, screw caps, foil or plastic covers, and the like; or other container known in the art. The compositions may be compact compositions, comprising less than about 15%, or less than about 10%, or less than about 7% water.
  • As used herein, “High charge density” means a charge density of greater than about 1 meq/g. “Low charge density” means a charge density of less than about 1 meq/g.
  • As used herein, the phrase “high molecular weight” means a molecular weight of greater than about 1,000,000 kD. The phrase “low molecular weight” means a molecular weight of from about 1,000 to about 500,000 kD.
  • As used herein, “isotropic” means a clear mixture, (having no visible haziness and/or dispersed particles) and having a uniform transparent appearance.
  • As used herein, “structured phase” means that portion of a composition comprising primary and/or colloidal particles when separated by centrifugation.
  • As used herein, the term “continuous phase” means that portion of a composition substantially free from particles upon separation by centrifugation.
  • As defined herein, “stable” means that no visible phase separation is observed for a period of at least about two weeks, or at least about four weeks, or greater than about a month or greater than about four months, as measured using the Floc Formation Test, described in USPA 2008/0263780 A1.
  • As defined herein, “unit dose” means an amount of fabric care composition suitable to treat one load of laundry, such as from about 0.05 to about 100 g, or from 10 to about 60 g, or from about 20 to about 40 g.
  • All measurements are performed at 25° C. unless otherwise specified.
  • The test methods disclosed in the present application should be used to determine the respective values of the parameters of Applicants' invention.
  • Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • Without being limited by theory, Applicants believe the cationic polymers of the disclosed compositions are useful for providing one or more fabric benefits, such as a color rejuvenation benefit, as a result of cationic polymer coalescence with anionic surfactant to form a coacervate system. This, in turn, is believed to deliver a benefit to the treated fabric without the necessity of dyes or other coloring agents via formation of a thin film on the fiber of the treated fabric. However, the direct combination, for example via simple mixing, of anionic surfactant and cationic polymers yields an unstable solution, wherein the surfactant and polymers aggregate to form an unstable composition with a rheology unsuitable for consumer use. Applicants have recognized that, by separating a mixture of cationic polymer and a mixture of anionic surfactant, and combining via a high energy milling step, surfactant-polymer particles of a certain size can be formed. Without being bound by theory, by forming particles of the dimensions disclosed herein, a stable, homogeneous solution containing cationic polymer and anionic surfactant can be achieved.
  • In one aspect, a process for preparing a composition comprising a structured phase and optionally, a continuous phase, is disclosed, wherein said process comprises the steps of
      • a. combining a polymer mixture comprising a cationic polymer, and a surfactant mixture comprising an anionic surfactant, using high energy dispersion to form a premix comprising particles comprising cationic polymer and anionic surfactant;
      • b. introducing a structurant into the premix using low energy dispersion to form a stable composition;
        • wherein said stable composition has a resting viscosity of from about 10,000 to about 50,000 cps or from about 20,000 to about 30,000 cps as measured at 0.05/s.
  • The dispersion energies of steps (a) and (b) can be characterized as having a certain Energy Density, wherein Energy Density is generated by exerting a power density on the feed within the mixing chamber for a residence time. Energy Density can be represented by the equation: E=W*ΔT, wherein E represents energy density, W represents power density, and ΔT represents residence time. Residence time means the average amount of time a fluid remains within the mixing chamber and is determined by calculating the active volume of the device where the fluid stream receives the highest concentration of power input divided by the flow rate of the stream out of the mixing chamber. The high energy dispersion step can be also be characterized by power density and residence time.
  • High Energy Dispersion Step—The energy level of the high energy dispersion step may be empirically determined by one of skill in the art, by analysis of the particle size and distribution of the second mixture and subsequent adjustment of the mixing energy applied when generating the mixture, provided the energy level is sufficient to achieve the primary particle size and distribution as described.
  • The disclosed processes use relatively high power density to achieve the desired colloid attributes. For mechanical high shear mixers, mixing power densities are in the range of 1 W/ml to 1000 W/ml. For high pressure drop mixing equipment (such as sonolators or valve homogenizers) power density ranges from about 1000 W/ml to about 100,000 W/ml (See “A Physical Interpretation of Drop Sizes in Homogenizers and Agitated Tanks, Including the Dispersion of Viscous Oils,” J. T. Davies, Chemical Engineering Science, Vol. 42, No 7, pp 1671-1676, 1987.
  • The energy level may be applied in an amount sufficient to achieve the primary particle size and distribution disclosed herein. In one aspect, the high energy dispersion step may have an Energy Density of from about 0.1 to about 100 J/ml, or from about 0.5 to about 50 J/ml, or from about 1 to about 10 J/ml.
  • In one aspect, the energy density may be generated from a power density of from about 0.01 to about 1,000,000 W/ml, or from about 0.1 to about 100,000 W/ml. The residence time may be from about 1 millisecond to about 10 seconds, or from about 1 millisecond to about 1 second, or from about 2 milliseconds to about 100 milliseconds.
  • In one aspect, the residence time may be less than 10 seconds and the power density may be greater than about 0.01 W/ml. In one aspect, the residence time may be less than 1 second and the power density may be greater than about 0.1 W/ml. In one aspect, the residence time may be less than 100 milliseconds and the power density may be greater than about 1 W/ml.
  • In one aspect, metered streams of the polymer mixture and surfactant mixture may be combined continuously in a pipe where the fluids are intimately contacted with each other in one or more high shear mechanical or static mixers. Mechanical mixers include rotor stator mills (e.g. manufactured by IKA, Silverson, Quadro-Ytron), colloid mills (IKA, Premier), Stirred Bead Mills (Romaco)). Static mixers may consist of an array of similar, stationary mixing elements, placed one behind the other in a pipe or channel (eg. manufactured for instance by Sulzer Ltd., Koch-Glitsch Inc., and Chemineer Inc). Static mixers suitable for this process also include orifice, microchannel or valve-type mixers. For instance, venturi mixers, microfluidizers (Microfluidics), Sonolator (Sonic Corp.), pressure homogenizers (BEEI, GEA Niro-Soavi, Arde Barinco, Niro). The polymer mixture may be contacted with the surfactant mixture in an agitated batch making tank to form the premix. To insure sufficient mixing, the polymer mixture may be injected into the high shear region of a high shear blender (e.g. IKA T-series batch high shear mixers). The mixing device energy may be any device, provided that sufficient energy is provided to create colloid particles of the desired composition, unit particle size, and particle birefringent optical characteristics. Fine mixing of the polymer mixture with the surfactant mixture results in the formation of primary particles having a primary particle size distribution as described above dispersed in the third mixture, or “premix.” Any larger than desired particles formed during blending can also be reduced in size by additional high shear milling steps. The premix can then be used for subsequent formulation as either a detergent, additive, rinse-added solution, or the like.
  • Low Energy Dispersion Step—The structurant may be incorporated into the third solution/premix with a low energy dispersion step sufficient to achieve adequate incorporation of structuring agents to aid in suspension of the colloid particles in the composition. Incorporation mixing processes can be in the form of continuous static mixers or batch tank agitation where power densities range from about 0.0001 W/ml to about 10 W/ml. In some cases, mechanical high shear mixers and constricted flow type (e.g. orifices) mixers with power densities of from about 1 W/ml to about 1000 W/ml can be used.
  • In one aspect, the low energy dispersion of step (b) has an energy density from about 0.001 to about 1 J/ml, or from about 0.1 to about 10 J/ml, or from about 0.005 to about 0.5 J/ml. In another aspect, the energy density is generated from a power density of from about 0.0001 W/ml to about 10 W/ml, alternatively from about 1 W/ml to about 1000 W/ml.
  • In one aspect, the low energy dispersion of step (b) may comprise an energy density generated from a power density of from about 0.01 to about 1,000,000 W/ml, or from about 0.1 to about 100,000 W/ml wherein the residence time may be from about 1 millisecond to about 10 seconds, or from about 1 millisecond to about 1 sec, or from about 2 milliseconds to about 100 ms. In one aspect, when the residence time is less than 10 seconds, the power density may be greater than about 0.01 W/ml. In one aspect, when the residence time is less than 1 second, the power density may be greater than about 0.1 W/ml. In one aspect, when the residence time is less than 100 milliseconds, the power density may be greater than about 1 W/ml.
  • For structurants that are shear-sensitive (i.e. those that lose structuring capability when subjected to high energy density processing) the energy input from the mixing device may be lowered so as to prevent damage to the structurant. Entrainment of air may be limited throughout the process.
  • Particles—In one aspect, the particles may comprise primary particles having a primary particle size of from about 0.05 to about 500 μm, or from about 0.1 to about 250 μm, or from about 0.5 to about 50 μm. In one aspect, from about 70% to about 100%, based on total number of primary particles, of the primary particles have a particle size within this range. In one aspect, the high energy dispersion step may form primary particles having a primary particle size distribution such that at least 70% of the primary particles, based on total number of primary particles, have a particle size of less than about 50 μm.
  • In one aspect, the particles may comprise colloidal particles, wherein the colloidal particles have a colloidal particle size from about 0.05 to about 1000 μm, or from about 0.5 to about 500 μm, or from about 1.0 to about 50 μm. In one aspect, from about 70% to about 100% of the colloidal particles, based on total number of colloidal particles, have a particle size within this range. In one aspect, the high energy dispersion step may form colloidal particles having a colloidal particle size distribution such that at least 70% of the colloidal particles, based on total number of colloidal particles, have a particle size of less than about 500 μm.
  • Polymer Mixture—In one aspect, the cationic polymer may comprise a cationic polymer produced by polymerization of ethylenically unsaturated monomers using a suitable initiator or catalyst. These are disclosed in WO 00/56849 and U.S. Pat. No. 6,642,200.
  • In one aspect, the cationic polymer may be selected from the group consisting of cationic or amphoteric polysaccharides, polyethyleneimine and its derivatives, a synthetic polymer made by polymerizing one or more cationic monomers selected from the group consisting of N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl methacrylate, N,N-dialkylaminoalkyl acrylamide, N,N-dialkylaminoalkylmethacrylamide, quaternized N,N dialkylaminoalkyl acrylate quaternized N,N-dialkylaminoalkyl methacrylate, quaternized N,N-dialkylaminoalkyl acrylamide, quaternized N,N-dialkylaminoalkylmethacrylamide, Methacryloamidopropylpentamethyl-1,3-propylene-2-ol-ammonium dichloride, N,N,N,N′,N′,N″,N″-heptamethyl-N″-3-(1-oxo-2-methyl-2- propenyl)aminopropyl-9-oxo-8-azo-decane-1,4,10-triammonium trichloride, vinylamine and its derivatives, allylamine and its derivatives, vinyl imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium chloride and combinations thereof. The cationic polymer may optionally comprise a second monomer selected from the group consisting of acrylamide, N,N-dialkyl acrylamide, methacrylamide, N,N-dialkylmethacrylamide, C1-C12 alkyl acrylate, C1-C12 hydroxyalkyl acrylate, polyalkylene glyol acrylate, C1-C12 alkyl methacrylate, C1-C12 hydroxyalkyl methacrylate, polyalkylene glycol methacrylate, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl caprolactam, and derivatives, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethane sulfonic acid (AMPS) and their salts. The polymer may be a terpolymer made from more than two monomers. The polymer may optionally be branched or cross-linked by using branching and crosslinking monomers. Branching and crosslinking monomers include ethylene glycoldiacrylate divinylbenzene, and butadiene. In one aspect, the cationic polymer may include those produced by polymerization of ethylenically unsaturated monomers using a suitable initiator or catalyst, such as those disclosed in WO 00/56849 and U.S. Pat. No. 6,642,200. In one aspect, the cationic polymer may comprise charge neutralizing anions such that the overall polymer is neutral under ambient conditions. Suitable counter ions include (in addition to anionic species generated during use) include chloride, bromide, sulfate, methylsulfate, sulfonate, methylsulfonate, carbonate, bicarbonate, formate, acetate, citrate, nitrate, and mixtures thereof.
  • In one aspect, the cationic polymer may be selected from the group consisting of poly(acrylamide-co-diallyldimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate) and its quaternized derivative, poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride-co-acrylic acid), poly(diallyldimethyl ammonium chloride), poly(vinylpyrrolidone-co-dimethylaminoethyl methacrylate), poly(ethyl methacrylate-co-quaternized dimethylaminoethyl methacrylate), poly(ethyl methacrylate-co-oleyl methacrylate-co-diethylaminoethyl methacrylate), poly(diallyldimethylammonium chloride-co-acrylic acid), poly(vinyl pyrrolidone-co-quaternized vinyl imidazole) and poly(acrylamide-co-methacryloamidopropyl-pentamethyl-1,3-propylene-2-ol-ammonium dichloride). These cationic polymers include and may be further described by the nomenclature Polyquaternium-1, Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-8, Polyquaternium-1, Polyquaternium-14, Polyquaternium-22, Polyquaternium-28, Polyquaternium-30, Polyquaternium-32 and Polyquaternium-33, as named under the International Nomenclature for Cosmetic Ingredients.
  • In one aspect, the cationic polymer may comprise a cationic acrylic based polymer. In one aspect, the cationic polymer may comprise a cationic polyacrylamide. In one aspect, the cationic polymer may comprise poly(acrylamide-N,N-dimethylaminoethyl acrylate) and its quaternized derivatives. In this aspect, the cationic polymer may be that sold under the tradename Sedipur®, available from BTC Specialty Chemicals, BASF Group, Florham Park, N.J.
  • In one aspect, the cationic polymer may comprise poly(acrylamide-co-methacrylamidopropyltrimethyl ammonium chloride).
  • In one aspect, the cationic polymer may comprise a non-acrylamide based polymer, such as that sold under the tradename Rheovis® CDE, available from Ciba Specialty Chemicals, a BASF group, Florham Park, N.J., or as disclosed in USPA 2006/0252668.
  • In one aspect, the cationic polymer may comprise polyethyleneimine or a polyethyleneimine derivative. In one aspect, the cationic polymer may be a polyethyleneinine such as that sold under the tradename Lupasol® by BASF, AG, Lugwigschaefen, Germany
  • In one aspect, the cationic polymer may include alkylamine-epichlorohydrin polymers, which are reaction products of amines and oligoamines with epicholorohydrin. These include those polymers listed in U.S. Pat. Nos. 6,642,200 and 6,551,986. Examples include dimethylamine-epichlorohydrin-ethylenediamine, and available under the trade name Cartafix® CB and Cartafix® TSF from Clariant, Basle, Switzerland.
  • In one aspect, the cationic polymer may comprise a synthetic cationic polymer comprising polyamidoamine-epichlorohydrin (PAE) resins of polyalkylenepolyamine with polycarboxylic acid. The most common PAE resins are the condensation products of diethylenetriamine with adipic acid followed by a subsequent reaction with epichlorohydrin. They are available from Hercules Inc. of Wilmington Del. under the trade name Kymene™ or from BASF AG (Ludwigshafen, Germany) under the trade name Luresin™. These polymers are described in Wet Strength resins and their applications edited by L. L. Chan, TAPPI Press (1994), at pp. 13-44.
  • In one aspect, the cationic polymer may be selected from the group consisting of cationic or amphoteric polysaccharides. In one aspect, the cationic polymer may comprise a polymer selected from the group consisting of cationic and amphoteric cellulose ethers, cationic or amphoteric galactomanan, cationic guar gum, cationic or amphoteric starch, and combinations thereof.
  • In one aspect, the cationic polymer may comprise an amphoteric polymer, provided the polymer possesses a net positive charge. Said polymer may have a cationic charge density of about 0.05 to about 18 milliequivalents/g.
  • In one aspect, the cationic polymer may have a cationic charge density of from about 0.005 to about 23 milliequivalents/g, from about 0.01 to about 12 milliequivalents/g, or from about 0.1 to about 7 milliequivalents/g, at the pH of the intended use of the composition. For amine-containing polymers, wherein the charge density depends on the pH of the composition, charge density is measured at the intended use pH of the product. Such pH will generally range from about 2 to about 11, more generally from about 2.5 to about 9.5. Charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit. The positive charges may be located on the backbone of the polymers and/or the side chains of polymers.
  • In one aspect, the cationic polymer may have a weight-average molecular weight of from about 500 to about 5,000,000 Daltons, or from about 1,000 to about 2,000,000 Daltons, or from about 2,500 to about 1,500,000 Daltons as determined by size exclusion chromatography relative to polyethyleneoxide standards with RI detection. In one aspect, the molecular weight of the cationic polymer may be from about 500 to about 37,500 kD. The cationic polymers may also range in both molecular weight and charge density. The cationic polymer may have a charge density of from about 0.05 to about 12 meq/g, or from about 1.0 to about 6 meq/q, or from about 3 to about 4 meq/g at a pH of from about 3 to about 9. In one aspect, the one or more cationic polymer may have a weight-average molecular weight of 500 to about 37,500 Daltons and a charge density of from about 0.1 meq/g to about 12.
  • In one aspect, the polymer mixture may have a viscosity of from about 1 to about 1,000, or from about 400 to about 800 cps at 20/s.
  • In one aspect, the polymer mixture may optionally include a surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, and combinations thereof.
  • In one aspect, the polymer mixture may be isotropic.
  • In one aspect, the polymer mixture may comprise a structurant.
  • Surfactant Mixture—In one aspect, the surfactant mixture may comprise anionic surfactant. Non-limiting examples of suitable anionic surfactants include those described in USPA 12/075333. In one aspect, the HLB value of the anionic surfactant may be from about 4 to about 14, or from about 8 to about 10, or about 9. In one aspect, the surfactant The surfactant mixture may be provided in the form of a solution comprising, based on total weight of the surfactant mixture, from about 10% to about 70% of a solvent. The solvent may comprise a low molecular weight water-miscible molecule. In one aspect, the solvent may be water.
  • In one aspect, the surfactant mixture may have a viscosity of from about 1 to about 1,000 cps at 20/s, or from about 400 to about 800 cps at 20/s, or about 400 cps at 20/s.
  • In one aspect, the surfactant mixture may have a pH of about 7.0. The pH may be adjusted, using any suitable pH adjusting agent.
  • In one aspect, the surfactant mixture may be isotropic.
  • In one aspect, the surfactant mixture may comprise a structurant.
  • The polymer and surfactant mixtures may be prepared by means familiar to those in the art. The polymer mixture and/or surfactant mixture can optionally include one or more adjunct ingredients as described herein.
  • Composition—In one aspect, the composition may comprise, based on total weight of the composition, from about 0.1% to about 30%, or from about 0.5% to about 20%, or from about 1.0% to about 10%, or from about 1.5% to about 8%, of a cationic polymer. In one aspect, the composition may comprise, based on total weight of the composition, of from about 2% to about 50%, or from about 5% to about 25%, or from about 12% to about 20% of an anionic surfactant. The anionic surfactant may comprise a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, zwitterionic surfactants, and combinations thereof. In one aspect, the composition may comprise, based on total weight of the composition, from about 1.0% to about 50%, or from about 7% to about 40%, or from about 10% to about 20% of alkylethoxysulfonate (AES). In one aspect, the composition may comprise, based on total weight of the composition, less than about 5%, or less than about 10%, or less than about 50% HLAS.
  • In one aspect, the composition may comprise, based on total weight of the composition, from about 0.001% to 1.0%, or from 0.05% to 0.5%, or from 0.1% to 0.3% of an external structurant. Suitable structurants include those described, for example, in USPAs 2007/169741B2 and 2005/0203213. In one aspect, the structurant may comprise hydrogenated castor oil, commercially available as under the trade name Thixin®.
  • In one aspect, the composition may have a resting (low shear) viscosity of greater than about 10,000 cps@0.05/s. In another aspect, the low shear viscosity may be from about 10,000 to about 225,000 cps@0.05/s, or from about 30,000 to about 100,000 cps@0.05/s, or from about 10,000 to about 50,000 cps@0.05/s.
  • In one aspect, the composition may comprise a dispersing agent. The composition may comprise, based on total weight of the composition, from about 0% to about 7%, or from about 0.1% to about 5%, or from about 0.2% to about 3% of a dispersing agent. In one aspect, the dispersing agent may be substantially water soluble. The dispersing agent may be present in the surfactant mixture, the polymer mixture, the premix, the final composition, or a combination thereof.
  • In one aspect, the dispersing agent may be a nonionic surfactant. Suitable nonionic surfactants include addition products of ethylene oxide and, optionally, propylene oxide, with fatty alcohols, fatty acids, fatty amines, etc. They may be referred to herein as ethoxylated fatty alcohols, ethoxylated fatty acids, and ethoxylated fatty amines. Any of the ethoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant. Suitable compounds include surfactants of the general formula: R1—Y—(C2H4O)Z—C2H4OH wherein R1 may be selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups, and primary, secondary and branched chain alkyl- and alkenyl substituted phenolic hydrocarbyl groups; said hydrocarbyl groups having a hydrocarbyl chain length of from about 8 to about 20, or from about 9 to about 18 carbon atoms. In the general formula for the ethoxylated nonionic surfactants herein Y may be —O—, —C(O)O—, or —O—, and in which R1, when present, have the meanings given hereinbefore, and z may be at least about 4, or about 7 to about 25.
  • In one aspect, the dispersing agent may include a material having the general formula: R1O(CH(R2)CH2O)x(CH2CH2O)yR3 or R1O(CH2CH2O)x(CH(R2)CH2O)yR3 wherein R1 may be defined as above; R2 may be a C1-C3 alkyl unit; R3 may be hydrogen or C1-C3 alkyl, wherein x is from 1 to 100, and wherein y is from 0 to 20. The individual alkoxy monomers may be arranged blockwise or randomly. Non-limiting examples include the Plurafac® surfactants from BASF. Other suitable dispersing agents include the so-called propyleneoxide/ethyleneoxide block copolymers, having the following general structure: HO(CH2CH2O)x(CH(CH3)CH2O)y (CH2CH2O)zH, wherein x is from 1 to 100, wherein y is from 0 to 20, and z is from 0 to 100. Such agents include the Pluronic® PE compounds available from BASF.
  • Adjunct ingredients—Adjunct ingredient may comprise a material selected from the group consisting of fatty acids, brighteners, chelating agents, dye transfer inhibiting agents, enzymes, enzyme stabilizers, and pearlescent agents. Such adjuncts may be suitable for use in the instant compositions and may be desirably incorporated in certain aspects. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use may be found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1. The adjunct ingredients may be provided in the surfactant mixture, the polymer mixture, the premix, the final composition, or any combination thereof.
  • The stability of compositions made according to the disclosed methods as compared to compositions made via simple mixing is set forth in Table 1.
  • TABLE 1
    Composition Stability
    Composition Process Used Phase Stability
    3% Merquat 100, 17% AES (anionic High energy Stable for 4
    surfactant) using water as a carrier dispersion months
    3% Merquat 100, 17% AES (anionic Simple mixing Phase split
    surfactant) using water as a carrier after 2 days
  • TABLE 2
    Composition properties and rheology
    Composition Formula I Formula I Formula I Formula I
    Process Simple Mixing High Energy High Energy High Energy
    Dispersion Step Dispersion Step Dispersion Step
    Primary 10-500 micron 2 to 10 micron 2 to 10 micron 2 to 10 micron
    Particle Size
    Aggregate Many 10 to 100 micron 10 to 100 micron 10 to 100 micron
    structures >100
    micron
    Structurant 0.1% 0.3%
    Trihydroxystearin Trihydroxystearin
    Visual Contains Smooth, fluid, Smooth fluid, Higher viscosity,
    Appearance chunks of solid- opaque- opaque- opaque
    like material translucent translucent
    Stability at Separates in 24 4 Days at least 2 weeks at least 4 months
    70 F. hrs
    Shear Rate 15,000 cps 6,500 cps 10,000 cps 50,000 cps
    0.1 s−1
    Shear Rate  1,200 cps 1,000 cps   600 cps  2,000 cps
    10 s−1
  • Test Methods
  • Particle sizing—Particle size and structure in neat product (i.e., undiluted composition as described herein) is determined via light microscopy. A drop of neat product is placed on a glass microscope slide and covered with a glass coverslip. The coacervate particles are identified by their birefringent nature indicating a liquid crystalline character. These coacervate particles can be identified from other possible particulates in the formulation both by this birefringent nature, and either by inspection of the formulation in the absence of cationic polymer, and hence, in the absence of coacervate formation, or by systematic evaluation of other components in the mixture. Quantification of primary and colloidal particle size is completed by image analysis of the microscopy pictures. Often enhanced contrast techniques are used to improve contrast between the coacervate particles and the surrounding liquid, including differential interference contrast, phase contrast, polarized light, and/or the use of fluorescent dyes. Additional droplets are imaged to ensure that the resulting images and particle sizes are representative of the entire mixture.
  • Particle size under dilution may be determined using microscopy (light microscopy as described above, or electron microscopy if the particles are too small to be visible by light microscopy) and/or laser scattering techniques such as laser diffraction with Mie theory, dynamic light scattering, or focused beam reflectance mode. Often these techniques are used together, in that microscopy is used to identify the coacervate particles from other possible particulates in solution and scattering techniques offer a more rapid quantification of particle size. The choice of scattering method depends on the particle size of interest and the concentration level of particles in solution. In dynamic light scattering (DLS), the fluctuations in scattered light due to Brownian motion of the particles are measured. These fluctuations are correlated to obtain a diffusion coefficient and therefore a hydrodynamic radius of particles. This technique is used when the particles are less than a few microns and the solution conditions are dilute. In laser diffraction, the light scattered by the particles is measured by a series of detectors placed at different angles. The use of back scattering detectors and Mie theory enables detection of particle sizes less than 1 micron. This technique can be utilized to measure particles over a broader size range compared to DLS, and resolution of two populations of particle sizes (such as primary and colloidal particles) can be determined provided the difference in sizes is significant enough. In a focused beam reflectance measurement (FBRM), a chord length distribution, which is a “fingerprint” of the particle size distribution, is obtained. In FBRM, a focused laser beam scans across particles in a circular path, and as the beam scans across particles the backscattered light is detected as pulses of light. The duration of the pulse is converted to a chord length, and by measuring thousands of chord lengths each second, the chord length distribution is generated. As in the case of laser diffraction, detection of two size populations can be obtained provided the differences in size is great enough. This technique is used when the particles are greater than approximately 1 micron and is particularly useful when the turbidity and/or particle concentration in solution is high.
  • Examples Example I
  • The base composition is made by adding the component materials of Table 3 into a dish bottom tank. The component materials are mixed by hand to minimize the amount of air entrapped in the mixture. Upon complete blending, the resulting base composition is clear and isotropic, having a viscosity of from about 200 to about 800 cPS at 20 s−1. 71 liters of base composition is then combined with 25 liters of the isotropic polymer solution. To form the polymer solution, the neat polymer (Nalco, Merquat 100, Homopolymer of diallyldimethyl ammonium chloride, polymer molecular weight of from about 100,000 to about 150,000, 40% active) is diluted with water to form an 11.9% active polymer solution. The base composition is delivered at a rate of 3500 g/min using a Waukesha Pump Model (00602) and the polymer solution is delivered at a rate of 1265 g/min using a Pump (Moyno, E4ASSF3-SKA). The polymer solution and base composition are delivered simultaneously to the head of mill (IKA DR2000/5, two fine grindsets, 50% energy setting). The polymer solution is delivered via a dip tube inserted into the tubing such that the polymer solution is delivered as close as possible to the top of the grind sets without touching, thereby eliminating any air gap between the polymer introduction and dispersion with the base composition. Upon mixing of the base composition and the polymer solution as described above, a mixture containing colloidal particles is formed. Successful attainment of the colloidal particles can be confirmed at this step wherein a dispersed phase of colloid particles suspended in the product is visible via microscopy, the colloidal particles having a diameter of from about 10 to 20 um. Successful attainment of the colloidal particles can also be verified via observation of visible regions of birefringence in the dispersed phase using cross Polared microscopy.
  • After the polymer solution stream and the base composition stream are combined as described above to obtain a mixture containing colloidal particles, 3.75 liters of Thixcin®, an organic derivative of castor oil, available from Elementis) is introduced at a flow rate of 190 g/min using a Waukesha pump similar to the base composition one (Waukesha, 00618?) The Thixcin® is incorporated at the output of the mill to ensure rapid dispersion of the structurant into the colloid product via-a static mixer (12 element SMX static mixer (1″ size) (Sulzer Chemtech). The mixing is complete when the product is passed through the 12 element 1″ diameter static mixer at a flow rate of 5kg's/min. The product is then transferred to a storage container. The final product has a rheology profile of about 20,000-50,000 at low shear (0.5 s−1) and about 200-600 cPS at higher shear (20 s−1). All processing steps are carried out at ambient temperatures (20° C.).
  • TABLE 3
    Base Composition Formulation
    Base
    Composition
    Component Material (wt %)
    C25 AE1.8S surfactant1 17.736%
    Sodium Hydroxide2 2.513%
    Monoethanol Amine3 2.217%
    1,2 Propanediol4 3.236%
    Diethylene Glycol5 1.419%
    DTPA (diethylene triamine penta acetate)6 0.443%
    Citric Acid7 2.956%
    Sodium Cumene sulfate8 1.552%
    C12-C18 Fatty Acid9 1.848%
    Ethoxylated tetraethylene pentaimine10 0.517%
    Ethanol11 2.483%
    Perfume 0.61%
    N4 Amine (N,N′-Bis(3- 0.04%
    aminopropyl)ethylenediamine)12
    Merquat 10013 25.316%
    Thixcin ® (organic derivative of castor oil)14 0.15%
    Water to 100%
    1Available from The Procter & Gamble Company.
    2Available from Sigma Aldrich.
    3Available from Sigma Aldrich.
    4Available from Sigma Aldrich.
    5Available from Sigma Aldrich.
    6Available from Sigma Aldrich.
    7Available from Archer Daniels Midland.
    8Available from Rutgers Organics.
    9Available from Twin Rivers.
    10Available from BASF.
    11Available from Mays Chemical.
    12Available from BASF.
    13Polymer available from Nalco; solution made according to Example I.
    14Available from Elementis.
  • TABLE 4
    Exemplary Detergent Formulations
    Formula
    Component 1 2 3 4 5 6 7 8 9 10
    Material Wt %
    Alkyl 5.0-20  20.1  20.5  18   15   20.1  20.1  15   20.1  20.1  20.1 
    Ethoxylate
    sulfate
    HLAS (1)  0-10.0
    MLAS (2) 0-5.0
    Alkyl 0-5.0 0.3 2.0 1.5 4.0 0.5 0.7 2.5 0.3 0.3 0.3
    Ethoxylate
    Lauryl 0-4.0 2.2
    trimethyl
    ammonium
    chloride (3)
    Citric Acid 0-5.0 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4
    C1218 TPK 0-5.0 2.1 0   5.0 10   2.1 2.1 2.1 2.1 2.1 2.1
    FA (4)
    Enzyme 54.5 0-1.0 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
    mg/g active (5)
    Natalase - 0-0.1 0.3
    200L
    Carezyme - 0-0.5 0.1  0.05 2.0
    0.5L
    Borax 0-3   0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
    Ca Formate 0-0.1
    ethoxylated 0-2.0 0.7 0.7 0.7 0.8 0.7 0.5 0.7
    tetraethylene
    pentaimine
    PE20 (6) 0-3.0 0.7 0.7 0.7 0.7 0.7 0.7 0.7 1.5 2.0 0.7
    DTPA (7) 0-1.0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    FWA-15 (8) 0-0.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
    Merquat 100 (9) 1.0-4.0   2.0 2.0 2.0 3.0 2.0 3.0 4.0 1.5
    Merquat 106 (10) 1.0-4.0   4.0
    Cartafix TSF (12) 0-3.0 2.0 2.0 2.0 1.0
    Merquat 5 (13) 2.0 3.0
    Polyvinyl 0.5 0.3
    Pyrrolidone
    PP5495 (14) 0-4.0 2.0 2.0 2.0 2.0 0.5 0.5 1.0
    Ethanol 0-4.0 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8
    PEG400 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
    1,2- 0-6.0 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8
    propanediol
    MEA (mono- 0-4.0 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
    ethanol amine)
    NaOH As Needed to pH 6-9
    Na Cumene 0-3.0 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8
    sulfonate
    Na formate 0-0.5 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
    Trihydroxyl- 0-0.5 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
    stearin
    Suds 0-1.0
    Suppressor
    Acusol OP 301 0-0.5
    opacifier
    N4 amine  0-0.02 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
    Perfume 0.3-2.5   1-2 1-2 1-2 1-2 1-2 1-2 1-2 1-2 1-2 1-2
    Water Balance to 100%
    (1) Linear alkylbenzene sulfonate.
    (2) Mid-chain branched linear alkylbenzene sulfonate.
    (3) lauryl trimethyl ammonium chloride.
    (4) Topped palm kernel fatty acid.
    (5) Protease, genetically engineered variant of the detergent protease from Bacillus Amyloliquifaciens.
    (6) polyethyleneimine MW600 EO20.
    (7) diethylene triamine penta acetate.
    (8) disodiuma 4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate.
    (9) Homopolymer of diallyldimethyl ammonium chloride, polymer molecular weight of from about 100,000 to about 150,000.
    (10) Homopolymer of diallyldimethyl ammonium chloride, polymer molecular weight from about 5,000 to about 15,000.
    (11) Co-polymer of dimethyldiallyl ammonium chloride and acrylic acid, molecular weight of about 450,000 to 550,000 Daltons.
    (12) Terpolymer of dimethylamine-epichlorohydrin-ethylenediamine.
    (13) Poly(acrylamide-co-methacryloyloxyethyltrimethyl ammonium methylsulfate)
    (14) Dimethyl, methyl (polyethylene oxide acetate capped) siloxane.
  • It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
  • The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”
  • Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
  • While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (19)

1. A process for preparing a composition comprising a structured phase and optionally, a continuous phase, comprising the steps of
a. combining a polymer mixture comprising a cationic polymer and a surfactant mixture comprising an anionic surfactant via high energy dispersion to form a premix comprising particles comprising cationic polymer and anionic surfactant;
b. introducing a structurant into said premix using low energy dispersion to form a stable composition;
wherein said stable composition has a resting viscosity of from about 10,000 to about 50,000 cps at 0.05/s.
2. A process according to claim 1 wherein said high energy dispersion of step (a) has an Energy Density of from about 0.1 to about 100 J/ml.
3. A process according to claim 1 wherein said high energy dispersion of step (a) is generated from a power density of from about 0.01 to about 1,000,000 W/ml, wherein the residence time is from about 1 millisecond to about 10 seconds.
4. A process according to claim 1 wherein said low energy dispersion of step (b) has an energy density from about 0.001 to about 1 J/ml.
5. A process according to claim 1 wherein said low energy dispersion of step (b) has an energy density generated from a power density of from about 0.01 to about 1,000,000 W/ml wherein the residence time may be from about 1 millisecond to about 10 seconds.
6. A process according to claim 1 wherein said particles comprise primary particles having a particle size of from about 0.05 to about 500 μm.
7. A process according to claim 1 wherein said particles comprise colloidal particles having a particle size of from about 0.05 to about 1000 μm.
8. A composition according to claim 1, wherein said polymer mixture comprises a cationic polymer selected from the group consisting of cationic polysaccharide, polyethyleneimine and its derivatives, poly(acrylamide-co-diallyldimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethylaminoethyl methacrylate) and its quaternized derivative, poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride-co-acrylic acid), poly(diallyldimethyl ammonium chloride), poly(vinylpyrrolidone-co-dimethylaminoethyl methacrylate), poly(ethyl methacrylate-co-quaternized dimethylaminoethyl methacrylate), poly(ethyl methacrylate-co-oleyl methacrylate-co-diethylaminoethyl methacrylate), poly(acrylate-co-methacrylamidopropyltrimethylammonium, poly(methacrylate-co-methacrylamidopropyltrimethylammonium, poly(diallyldimethylammonium chloride-co-acrylic acid), poly(vinyl pyrrolidone-co-quaternized vinyl imidazole) and poly(acrylamide-co-methacryloamidopropyl-pentamethyl-1,3-propylene-2-ol-ammonium dichloride), and mixtures thereof.
9. A composition according to claim 1 wherein said mixture comprises poly(diallyldimethylammonium chloride-co-acrylic acid).
10. A process according to claim 1, wherein said polymer mixture comprises a cationic polymer having a charge density of from about 0.05 to about 7 meq/g at a pH of from about 3 to about 9.
11. A process according to claim 1, wherein said polymer mixture comprises a cationic polymer having a weight average molecular weight of from about 500 to about 10,000,000 Daltons.
12. A process according to claim 1, wherein said polymer mixture comprises a cationic polymer having a weight-average molecular weight less than 37,500 Daltons and a charge density greater than about 5 meq/g.
13. A process according to claim 1 wherein the polymer mixture has a viscosity of from about 1 to about 1,000 cps at 20/sec.
14. A process according to claim 1 wherein the polymer mixture is isotropic.
15. A process according to claim 1 wherein the polymer mixture comprises a surfactant.
16. A process according to claim 1, wherein said surfactant mixture comprises a surfactant having an HLB of from about 4 to about 14.
17. A process according to claim 1, wherein said surfactant mixture comprises alkylethoxylated sulfate.
18. A process according to claim 1 wherein said surfactant mixture is isotropic.
19. A process according to claim 1 wherein one or both of the polymer mixture and/or surfactant mixture comprises a dispersing agent.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100144579A1 (en) * 2007-08-08 2010-06-10 Volkel Theodor Color-Safe Detergent or Cleaning Agent having Optical Brightener
US20140352076A1 (en) * 2013-05-31 2014-12-04 Haiyan Song Laundry detergents
WO2016200440A1 (en) 2015-06-11 2016-12-15 The Procter & Gamble Company Device and methods for applying compositions to surfaces
US20170166843A1 (en) * 2015-12-10 2017-06-15 The Procter & Gamble Company Process of making a liquid laundry detergent composition
US20190048296A1 (en) * 2017-08-10 2019-02-14 Henkel IP & Holding GmbH Unit dose detergent products with improved pac rigidity
US10927324B1 (en) * 2019-08-28 2021-02-23 Henkel IP & Holding GmbH Unit-dose detergent compositions containing polyethylene glycol and an organic acid

Families Citing this family (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2318500B1 (en) 2008-08-28 2018-02-28 The Procter and Gamble Company Methods for providing a benefit
EP2449077A1 (en) * 2009-06-30 2012-05-09 The Procter & Gamble Company Fabric care compositions, process of making, and method of use
PT2365123E (en) * 2010-03-09 2013-03-11 Clariant Finance Bvi Ltd Combined warp sizing and fixing agent and new method for fixing sulfur dyestuffs on warp
CN102939367A (en) * 2010-05-14 2013-02-20 太阳产品公司 Polymer-containing cleaning compositions and methods of production and use thereof
BR112012029742A2 (en) * 2010-06-09 2016-08-09 Procter & Gamble nonionic surfactant stable dispersion preparation method for personal care
ES2516818T3 (en) 2010-06-09 2014-10-31 The Procter & Gamble Company Fluid mixing unit and method for mixing a liquid composition
FR2961522B1 (en) * 2010-06-18 2013-03-15 Rhodia Operations PROTECTION OF THE COLORING OF TEXTILE FIBERS BY CATIONIC POLYSACCHARIDES
US10273434B2 (en) 2010-06-18 2019-04-30 Rhodia Operations Protection of the color of textile fibers by means of cationic polysacchrides
US9034813B2 (en) 2010-09-17 2015-05-19 Ecolab Usa Inc. High performance low viscoelasticity foaming detergent compositions employing extended chain anionic surfactants
US20140030304A1 (en) * 2011-04-08 2014-01-30 Basf Se Process for the Treatment of Synthetic Textiles with Cationic Biocides
WO2013070560A1 (en) * 2011-11-11 2013-05-16 The Procter & Gamble Company Surface treatment compositions including shielding salts
US20140020188A1 (en) * 2012-07-19 2014-01-23 The Procter & Gamble Company Compositions comprising hydrophobically modified cationic polymers
EP2690210A1 (en) * 2012-07-27 2014-01-29 Whirlpool Corporation Method for washing coloured clothes in a domestic washing machine
US9157049B2 (en) 2012-11-28 2015-10-13 Ecolab Usa Inc. Viscoelastic surfactant based cleaning compositions
US9029313B2 (en) 2012-11-28 2015-05-12 Ecolab Usa Inc. Acidic viscoelastic surfactant based cleaning compositions comprising glutamic acid diacetate
ES2744246T3 (en) 2012-11-28 2020-02-24 Ecolab Usa Inc Foam stabilization with polyethyleneimine ethoxylates
US10773973B2 (en) 2013-03-08 2020-09-15 Ecolab Usa Inc. Enhanced foam removal of total suspended solids and multiply charged cations from aqueous or aqueous/oil mixed phase via increased viscoelasticity
US8759277B1 (en) 2013-03-08 2014-06-24 Ecolab Usa Inc. Foam stabilization and oily soil removal with associative thickeners
US10435308B2 (en) 2013-03-08 2019-10-08 Ecolab Usa Inc. Enhanced foam fractionation of oil phase from aqueous/oil mixed phase via increased viscoelasticity
US9758914B2 (en) 2013-03-15 2017-09-12 Whirlpool Corporation Methods and compositions for treating laundry items
US9702074B2 (en) 2013-03-15 2017-07-11 Whirlpool Corporation Methods and compositions for treating laundry items
WO2015143644A1 (en) * 2014-03-26 2015-10-01 The Procter & Gamble Company Cleaning compositions containing cationic polymers, and methods of making and using same
WO2015143997A1 (en) * 2014-03-26 2015-10-01 The Procter & Gamble Company Cleaning compositions containing cationic polymers, and methods of making and using same
WO2016127387A1 (en) * 2015-02-13 2016-08-18 The Procter & Gamble Company Cleaning compositions containing alkyl sulfate surfactants and cationic polymer for holistic improvement of sudsing profile
US9862912B2 (en) 2014-03-26 2018-01-09 The Procter & Gamble Company Cleaning compositions containing cationic polymers, and methods of making and using same
WO2015200809A1 (en) * 2014-06-27 2015-12-30 Ecolab Usa Inc. High performance low viscoelasticity foaming detergent compositions employing extended chain anionic surfactants
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CN113817551B (en) * 2021-11-03 2024-03-01 广州立白企业集团有限公司 Laundry soap containing cationic polymer
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Citations (90)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549546A (en) * 1967-10-02 1970-12-22 Procter & Gamble Process for preparing liquid detergent
US3943255A (en) * 1974-05-22 1976-03-09 Nalco Chemical Company Alkyl polymaine microbiocides
US4622161A (en) * 1983-10-03 1986-11-11 Akzo N.V. Dosing unit comprising a detergent and/or a bleaching agent
US4634544A (en) * 1984-04-09 1987-01-06 Henkel Kommanditgesellschaft Auf Aktien Detergent composition for colored fabrics
US4772462A (en) * 1986-10-27 1988-09-20 Calgon Corporation Hair products containing dimethyl diallyl ammonium chloride/acrylic acid-type polymers
US4806522A (en) * 1988-01-28 1989-02-21 International Flavors & Fragrances Inc. 2-alkanoyl-2-(1-penten-1-yl)cyclohexanones, process for preparing same, and organoleptic uses thereof and intermediates useful in said process
US5476660A (en) * 1994-08-03 1995-12-19 Lever Brothers Company, Division Of Conopco, Inc. Deposition of materials to surfaces using zwitterionic carrier particles
US5529696A (en) * 1995-07-20 1996-06-25 Diversey Corporation Method of laundering items and purifying waste water therefrom
US5573709A (en) * 1990-12-05 1996-11-12 Procter & Gamble Shampoo compositions with silicone and cationic organic polymeric conditioning agents
US5814596A (en) * 1994-06-24 1998-09-29 The Procter & Gamble Company Structured detergent pastes and a method for manufacturing detergent particles from such pastes
US5885948A (en) * 1995-02-15 1999-03-23 The Procter & Gamble Company Crystalline hydroxy waxes as oil in water stabilizers for skin cleansing liquid composition
US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
US5955415A (en) * 1997-08-04 1999-09-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polyethyleneimines for enhanced peroxygen bleach stability
US6156720A (en) * 1998-06-23 2000-12-05 Basf Aktiengesellschaft Propoxylated/ethoxylated polyalkyleneimine dispersants
US6255271B1 (en) * 1998-09-16 2001-07-03 Unilever Home & Personal Care, Usa, Division Of Conopco Fabric care composition
US20010034316A1 (en) * 2000-02-25 2001-10-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric care composition
US20010051142A1 (en) * 2000-03-21 2001-12-13 Duden Carol A. Conditioning compositions
US20020010121A1 (en) * 2000-03-01 2002-01-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleaching and dye transfer inhibiting composition and method for laundry fabrics
US20020010124A1 (en) * 2000-04-12 2002-01-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Laundry wash compositions
US20020055451A1 (en) * 2000-09-08 2002-05-09 Ditmar Kischkel Detergent tablets
US20020058604A1 (en) * 2000-09-08 2002-05-16 Ditmar Kischkel Laundry detergent tablets
US6533873B1 (en) * 1999-09-10 2003-03-18 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Suspending clear cleansing formulation
US20030053980A1 (en) * 2001-04-30 2003-03-20 The Gillette Company Shaving compositions containing highly lubricious water soluble polymers
US6546797B2 (en) * 2000-08-24 2003-04-15 Mlho, Inc. Absolute position measure with multi-beam optical encoding
US6569823B2 (en) * 2000-04-14 2003-05-27 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Fabric care composition
US6573229B2 (en) * 2000-04-12 2003-06-03 Unilever Home & Personal Care Usa Division Of Conopco Inc. Laundry wash compositions
US20030104964A1 (en) * 1996-09-19 2003-06-05 The Procter & Gamble Company Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US6576228B1 (en) * 2000-03-10 2003-06-10 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Personal wash sunscreen compositions which deposit and lather well
US20030109400A1 (en) * 2001-10-26 2003-06-12 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Care booster composition for supplementing the performance of laundry compositions
US6620209B2 (en) * 2000-09-08 2003-09-16 Cognis Deutschland Gmbh & Co. Kg Laundry detergent compositions
US20030192130A1 (en) * 2002-04-09 2003-10-16 Kaaret Thomas Walter Fabric treatment for stain release
US20040023836A1 (en) * 2000-09-01 2004-02-05 David Moorfield Fabric care composition
US20040033924A1 (en) * 2002-08-14 2004-02-19 Murphy Dennis Stephen Methods for conferring fabric care benefits during laundering
US20040063597A1 (en) * 2002-09-27 2004-04-01 Adair Matha J. Fabric care compositions
US20040071742A1 (en) * 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals
US20040071746A1 (en) * 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals
US20040092425A1 (en) * 2002-11-04 2004-05-13 The Procter & Gamble Company Liquid laundry detergent
US6740633B2 (en) * 2000-05-09 2004-05-25 Basf Aktiengesellschaft Polyelectrolyte complexes and a method for production thereof
US20040139559A1 (en) * 2001-05-18 2004-07-22 Juergen Detering Hydrophobically modified polyethylenimines and polyvinylamines for wrinkle-resistant finishing of textiles containing cellulose
US20040152616A1 (en) * 2003-02-03 2004-08-05 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Laundry cleansing and conditioning compositions
US20040186030A1 (en) * 2003-01-27 2004-09-23 The Procter & Gamble Company Personal cleansing composition containing irregularly shaped particles and spherical particles
US20040220063A1 (en) * 2002-02-20 2004-11-04 Chappell Michael Jahi Personal cleansing compositions
US6846797B1 (en) * 1999-10-01 2005-01-25 Unilever Home & Personal Care Usa A Division Of Conopco, Inc. Fabric care composition comprising an epichlorohydrin resin and anionic polymer
US20050028293A1 (en) * 2002-09-09 2005-02-10 Cedric Geffroy Rinsing formulation for textiles
US20050097678A1 (en) * 2002-09-09 2005-05-12 Cedric Geffroy Polymer-based formulation for textile rinsing
US20050101505A1 (en) * 2003-11-06 2005-05-12 Daniel Wood Liquid laundry detergent composition having improved color-care properties
US6894017B2 (en) * 2001-11-01 2005-05-17 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Liquid detergent compositions
US6897017B1 (en) * 1997-01-31 2005-05-24 Odyssey Thera Inc. Vivo library-versus-library selection of optimized protein-protein interactions
US6903064B1 (en) * 1999-05-26 2005-06-07 Procter & Gamble Company Detergent composition comprising polymeric suds volume and suds duration enhancers
US6908490B2 (en) * 2000-06-06 2005-06-21 Basf Aktiengesellschaft Use of cationically modified, particle-shaped, hydrophobic polymers as addition agents in textile rinsing or care products and as addition agents in detergents
US20050153852A1 (en) * 2003-11-04 2005-07-14 Evans Erica L. Personal cleaning compositions
US20050153865A1 (en) * 2002-04-09 2005-07-14 Detering Juergen Cationically modified, anionic polyurethane dispersions
US20050158489A1 (en) * 2003-12-17 2005-07-21 Fuji Photo Film Co., Ltd. Ink-jet recording medium and process for producing the same
US20050159330A1 (en) * 2004-01-16 2005-07-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent composition
US20060003913A1 (en) * 2004-06-30 2006-01-05 The Procter & Gamble Company Perfumed liquid laundry detergent compositions with functionalized silicone fabric care agents
US20060021150A1 (en) * 2004-07-27 2006-02-02 Cheng Hu Durable treatment for fabrics
US20060030513A1 (en) * 2004-08-03 2006-02-09 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Softening laundry detergent
US20060029625A1 (en) * 2004-08-06 2006-02-09 Niebauer Michael F Personal cleansing composition containing fibers
US7012054B2 (en) * 2003-12-03 2006-03-14 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Softening laundry detergent
US20060074005A1 (en) * 2004-10-05 2006-04-06 Ditmar Kischkel Liquid surfactant mixtures
US20060079422A1 (en) * 2004-10-08 2006-04-13 Sanjeev Midha Personal care composition containing a cleansing phase and a benefit phase
US20060083761A1 (en) * 2004-10-15 2006-04-20 The Procter & Gamble Company Personal care compositions comprising visible beads, cationic polymer, and surfactant
US7074750B2 (en) * 2001-06-15 2006-07-11 Basf Aktiengesellschaft Treatment method, which promotes the removal of dirt, for the surfaces of textiles and non-textiles
US20060154836A1 (en) * 2005-01-12 2006-07-13 Amcol International Corporation Detersive compositions containing hydrophobic benefit agents pre-emulsified using sub-micrometer-sized insoluble cationic particles
US7091167B2 (en) * 2001-03-03 2006-08-15 Clariant Gmbh Laundry detergents and laundry treatment compositions comprising dye-transfer-inhibiting dye fixatives
US20060183662A1 (en) * 2005-02-16 2006-08-17 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid cleansing composition with unique sensory properties
US20060199756A1 (en) * 2005-03-04 2006-09-07 Creamer Marianne P Laundry compositions and their use
US20060217288A1 (en) * 2005-02-17 2006-09-28 Wahl Errol H Fabric care composition
US20060276370A1 (en) * 2005-06-03 2006-12-07 The Procter & Gamble Company Fabric care compositions
US20060287216A1 (en) * 2002-12-23 2006-12-21 Zhiqiang Song Hydrophobically Modified Polymers as Laundry Additives
US20070027050A1 (en) * 2005-07-27 2007-02-01 Conopco, Inc., D/B/A Unilever Liquid cleansing composition
US20070060489A1 (en) * 2005-02-17 2007-03-15 Sun James Z Cationic surfactant shampoo composition
US20070077221A1 (en) * 2005-06-23 2007-04-05 Aline Seigneurin Cosmetic composition comprising an ampholytic copolymer and another agent
US20070190009A1 (en) * 2004-10-22 2007-08-16 Shiseido Co., Ltd. Hair Cosmetic Composition
US7304026B2 (en) * 2004-04-15 2007-12-04 Colgate-Palmolive Company Fabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient
US20070277327A1 (en) * 2004-04-08 2007-12-06 Clariant Produkte (Deutschland) Gmbh Detergent And Cleaning Agents Containing Dye Fixatives And Soil Release Polymers
US20070292380A1 (en) * 2006-06-16 2007-12-20 James Anthony Staudigel Hair conditioning composition containing a non-guar galactomannan polymer derivative
US20080096788A1 (en) * 2004-10-20 2008-04-24 Frank-Peter Lang Liquid Detergent Comprising Anionic Surfactants and Colour Fixing Agent
US20080103081A1 (en) * 2004-10-23 2008-05-01 Clariant Produkte (Deutschland) Gmbh Brueningstrasse 50 Liquid Detergents Containing Colour Fixing Agents
US20080103080A1 (en) * 2004-09-10 2008-05-01 Frank-Peter Lang Liquid Washing Agent Containing a Color Fixing Agent
US20080131390A1 (en) * 2004-11-09 2008-06-05 Frank-Peter Lang Hair Treatment Product Containing Anionic Surfactants and Cationic Polymers
US20080160093A1 (en) * 2003-03-18 2008-07-03 James Robert Schwartz Composition comprising particulate zinc materials having a defined crystallite size
US20080234165A1 (en) * 2007-03-20 2008-09-25 Rajan Keshav Panandiker Liquid laundry detergent compositions comprising performance boosters
US20080261845A1 (en) * 2007-04-20 2008-10-23 Kao Corporation Skin cleansing compositions
US20090036339A1 (en) * 2007-03-30 2009-02-05 Anne Sans Mild, foaming cleansing composition
US20090048137A1 (en) * 2004-10-20 2009-02-19 Frank-Peter Lang Liquid detergent comprising secondary alkyl sulphonates and colour fixing agent
US20090297463A1 (en) * 2005-04-29 2009-12-03 Andrei Serveevich Bureiko Micelle Thickening Systems for Hair Colourant and Bleaching Compositions
US20100105592A1 (en) * 2005-08-04 2010-04-29 Mitsubishi Chemical Corporation Copolymer and detergent compositions containing the same
US20100307523A1 (en) * 2003-05-01 2010-12-09 Karl Shiqing Wei Striped liquid personal cleansing compositions containing a cleansing phase and a separate benefit phase comprising a high internal phase emulsion
US20100310644A1 (en) * 2007-12-21 2010-12-09 BASF ,Trademarks and Licenses Anti-dandruff compositions containing peptides

Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL133334C (en) 1964-06-19 1900-01-01
DE2934228A1 (en) 1979-08-24 1981-03-12 Basf Ag METHOD FOR THE QUANTITATIVE DETERMINATION OF THE SURFACE CHARGING OF SERUM LIPOPROTEINS.
ZA856442B (en) 1984-09-04 1987-04-29 Colgate Palmolive Co Wash cycle detergent-softener compositions having improved fabric subtanctivity
DD272191A3 (en) 1986-10-06 1989-10-04 Akad Wissenschaften Ddr METHOD FOR PRODUCING WATER-SOLUBLE HIGH-BRANCHED HIGH-MOLECULAR QUARTAKY POLYAMONIUM SALT
US4818421A (en) 1987-09-17 1989-04-04 Colgate-Palmolive Co. Fabric softening detergent composition and article comprising such composition
US4911852A (en) 1988-10-07 1990-03-27 The Procter & Gamble Company Liquid laundry detergent with curable amine functional silicone for fabric wrinkle reduction
JP2672881B2 (en) 1990-06-13 1997-11-05 花王株式会社 Liquid soft finish
GB9512836D0 (en) 1995-06-23 1995-08-23 Unilever Plc Fabric conditioning composition
CA2220104C (en) 1996-03-04 2002-07-09 Osi Specialties, Inc. Silicone aminopolyalkyleneoxide block copolymers
US6133227A (en) * 1997-06-23 2000-10-17 The Procter & Gamble Company Enzymatic detergent compositions
ATE269894T1 (en) * 1997-07-29 2004-07-15 Procter & Gamble AQUEOUS GEL DETERGENT COMPOSITIONS FOR LAUNDRY
JPH11148093A (en) 1997-11-18 1999-06-02 Kao Corp Detergent composition
GB9820554D0 (en) 1998-09-21 1998-11-11 Unilever Plc Use of cationic materials and compositions
AR023155A1 (en) 1999-03-25 2002-09-04 Procter & Gamble COMPOSITIONS FOR THE MAINTENANCE OF THE FABRIC THAT INCLUDE CERTAIN POLYMERS FOR THE TREATMENT OF THE FABRIC, CATIONICALLY LOADED
US6642200B1 (en) 1999-03-25 2003-11-04 The Procter & Gamble Company Fabric maintenance compositions comprising certain cationically charged fabric maintenance polymers
JP3407688B2 (en) 1999-03-29 2003-05-19 日本製紙株式会社 Recording sheet
DE19920118B4 (en) 1999-05-03 2016-08-11 Henkel Ag & Co. Kgaa Detergent tablets with coating and process for its preparation
JP2001107083A (en) 1999-10-06 2001-04-17 Kao Corp Detergent composition
US6551986B1 (en) 2000-02-16 2003-04-22 The Procter & Gamble Company Fabric enhancement compositions
GB0009059D0 (en) 2000-04-12 2000-05-31 Unilever Plc Use of polymers in laundry cleaners
JP2002060788A (en) 2000-08-23 2002-02-26 Kao Corp Liquid detergent composition
JP2002060800A (en) 2000-08-23 2002-02-26 Kao Corp Liquid detergent composition
JP2002060789A (en) 2000-08-23 2002-02-26 Kao Corp Detergent composition
JP2002060791A (en) 2000-08-23 2002-02-26 Kao Corp Liquid detergent composition
US6903061B2 (en) 2000-08-28 2005-06-07 The Procter & Gamble Company Fabric care and perfume compositions and systems comprising cationic silicones and methods employing same
US20050098759A1 (en) 2000-09-07 2005-05-12 Frankenbach Gayle M. Methods for improving the performance of fabric wrinkle control compositions
DE10064635A1 (en) 2000-12-22 2002-07-04 Henkel Kgaa Detergent tablets with delayed solubility comprise compressed particulate detergents ingredients including builder(s) and surfactant(s)
FR2820032B1 (en) * 2001-01-26 2003-05-02 Oreal OXIDATION DYE COMPOSITION FOR KERATIN FIBERS COMPRISING A CATIONIC POLY(VINYLLACTAM)
DE10116491A1 (en) 2001-04-03 2002-10-10 Cognis Deutschland Gmbh Textile conditioning composition, giving soft handle and increased hydrophilicity especially on polyacrylamide fabrics, comprising ester-quat, dimethyl diallylammonium chloride-acrylamide copolymer and water
US7524807B2 (en) * 2002-11-01 2009-04-28 The Procter & Gamble Company Rinse-off personal care compositions comprising anionic and/or nonionic perfume polymeric particles
BRPI0407114B1 (en) 2003-02-03 2018-09-11 Unilever Nv laundry composition
MXPA06004825A (en) 2003-10-31 2006-07-03 Procter & Gamble Fabric care compositions comprising aminosilicone.
US20050158270A1 (en) * 2004-01-15 2005-07-21 Seren Frantz Pearlizer concentrate and its use in personal care compositions
JP2007531816A (en) 2004-04-16 2007-11-08 ザ プロクター アンド ギャンブル カンパニー Liquid laundry detergent composition comprising a silicone blend as a fabric care agent
JP2006022203A (en) 2004-07-08 2006-01-26 Kao Corp Liquid detergent composition
JP2006114149A (en) 2004-10-15 2006-04-27 Fujitsu Ltd Semiconductor test system
DE102004051715A1 (en) 2004-10-23 2005-06-30 Clariant Gmbh Stable liquid detergent or cleansing compositions, especially for washing textiles, containing anionic and nonionic surfactants, soap and dye fixing agent, e.g. diallyl dimethylammonium chloride (co)polymer
AT501416B1 (en) 2005-02-15 2007-11-15 Leopold Franzens Uni Innsbruck METHOD AND SUBSTANCE MIXTURE FOR INCREASING THE SURFACE ACCURACY OF HYDROPHOBIC POLYMERS
JP4615600B2 (en) 2005-04-18 2011-01-19 ザ プロクター アンド ギャンブル カンパニー Diluted fabric care composition containing thickener and fabric care composition for use in the presence of anionic carryover
WO2006130709A2 (en) * 2005-06-01 2006-12-07 Rhodia Inc. Coacervate systems having soil anti-adhesion and anti-deposition properties on hydrophilic surfaces
WO2006134044A1 (en) 2005-06-15 2006-12-21 Ciba Specialty Chemicals Holding Inc. Laundering process for whitening synthetic textiles
JP2007031900A (en) 2005-07-28 2007-02-08 Lion Corp Liquid softening agent composition stored in transparent or translucent container
DE102005039168A1 (en) 2005-08-17 2007-02-22 Cognis Ip Management Gmbh Solid agents containing cationic polymers
WO2007101059A2 (en) * 2006-02-24 2007-09-07 Lubrizol Advanced Materials, Inc. Polymers containing silicone copolyol macromers and personal care compositions containing same
GB0605512D0 (en) * 2006-03-18 2006-04-26 Unilever Plc Fabric treatment composition and process for preparation thereof
CN101501171A (en) 2006-08-08 2009-08-05 宝洁公司 Fabric enhancing compositions comprising nano-sized particles and anionic detergent carry over tollerance
GB0617024D0 (en) * 2006-08-30 2006-10-11 Unilever Plc Hair treatment compositions incorporating hair substantive polymers
US8349300B2 (en) * 2007-04-19 2013-01-08 The Procter & Gamble Company Personal care compositions containing at least two cationic polymers and an anionic surfactant

Patent Citations (95)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549546A (en) * 1967-10-02 1970-12-22 Procter & Gamble Process for preparing liquid detergent
US3943255A (en) * 1974-05-22 1976-03-09 Nalco Chemical Company Alkyl polymaine microbiocides
US4622161A (en) * 1983-10-03 1986-11-11 Akzo N.V. Dosing unit comprising a detergent and/or a bleaching agent
US4634544A (en) * 1984-04-09 1987-01-06 Henkel Kommanditgesellschaft Auf Aktien Detergent composition for colored fabrics
US4772462A (en) * 1986-10-27 1988-09-20 Calgon Corporation Hair products containing dimethyl diallyl ammonium chloride/acrylic acid-type polymers
US4806522A (en) * 1988-01-28 1989-02-21 International Flavors & Fragrances Inc. 2-alkanoyl-2-(1-penten-1-yl)cyclohexanones, process for preparing same, and organoleptic uses thereof and intermediates useful in said process
US5573709A (en) * 1990-12-05 1996-11-12 Procter & Gamble Shampoo compositions with silicone and cationic organic polymeric conditioning agents
US5814596A (en) * 1994-06-24 1998-09-29 The Procter & Gamble Company Structured detergent pastes and a method for manufacturing detergent particles from such pastes
US5476660A (en) * 1994-08-03 1995-12-19 Lever Brothers Company, Division Of Conopco, Inc. Deposition of materials to surfaces using zwitterionic carrier particles
US5885948A (en) * 1995-02-15 1999-03-23 The Procter & Gamble Company Crystalline hydroxy waxes as oil in water stabilizers for skin cleansing liquid composition
US5529696A (en) * 1995-07-20 1996-06-25 Diversey Corporation Method of laundering items and purifying waste water therefrom
US20030104964A1 (en) * 1996-09-19 2003-06-05 The Procter & Gamble Company Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US6897017B1 (en) * 1997-01-31 2005-05-24 Odyssey Thera Inc. Vivo library-versus-library selection of optimized protein-protein interactions
US5955415A (en) * 1997-08-04 1999-09-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polyethyleneimines for enhanced peroxygen bleach stability
US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
US6300304B1 (en) * 1998-06-23 2001-10-09 Basf Aktiengesellschaft Propoxylated/ethoxylated polyalkyleneimine dispersants
US6156720A (en) * 1998-06-23 2000-12-05 Basf Aktiengesellschaft Propoxylated/ethoxylated polyalkyleneimine dispersants
US6255271B1 (en) * 1998-09-16 2001-07-03 Unilever Home & Personal Care, Usa, Division Of Conopco Fabric care composition
US6277810B2 (en) * 1998-09-16 2001-08-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dryer-added fabric care compositions containing amide-epichlorohydrin resins
US6903064B1 (en) * 1999-05-26 2005-06-07 Procter & Gamble Company Detergent composition comprising polymeric suds volume and suds duration enhancers
US6533873B1 (en) * 1999-09-10 2003-03-18 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Suspending clear cleansing formulation
US6846797B1 (en) * 1999-10-01 2005-01-25 Unilever Home & Personal Care Usa A Division Of Conopco, Inc. Fabric care composition comprising an epichlorohydrin resin and anionic polymer
US20010034316A1 (en) * 2000-02-25 2001-10-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric care composition
US20020010121A1 (en) * 2000-03-01 2002-01-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleaching and dye transfer inhibiting composition and method for laundry fabrics
US6576228B1 (en) * 2000-03-10 2003-06-10 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Personal wash sunscreen compositions which deposit and lather well
US20010051142A1 (en) * 2000-03-21 2001-12-13 Duden Carol A. Conditioning compositions
US6573229B2 (en) * 2000-04-12 2003-06-03 Unilever Home & Personal Care Usa Division Of Conopco Inc. Laundry wash compositions
US20020010124A1 (en) * 2000-04-12 2002-01-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Laundry wash compositions
US6569823B2 (en) * 2000-04-14 2003-05-27 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Fabric care composition
US6740633B2 (en) * 2000-05-09 2004-05-25 Basf Aktiengesellschaft Polyelectrolyte complexes and a method for production thereof
US6908490B2 (en) * 2000-06-06 2005-06-21 Basf Aktiengesellschaft Use of cationically modified, particle-shaped, hydrophobic polymers as addition agents in textile rinsing or care products and as addition agents in detergents
US6546797B2 (en) * 2000-08-24 2003-04-15 Mlho, Inc. Absolute position measure with multi-beam optical encoding
US20040023836A1 (en) * 2000-09-01 2004-02-05 David Moorfield Fabric care composition
US20020058604A1 (en) * 2000-09-08 2002-05-16 Ditmar Kischkel Laundry detergent tablets
US20020055451A1 (en) * 2000-09-08 2002-05-09 Ditmar Kischkel Detergent tablets
US6620209B2 (en) * 2000-09-08 2003-09-16 Cognis Deutschland Gmbh & Co. Kg Laundry detergent compositions
US7091167B2 (en) * 2001-03-03 2006-08-15 Clariant Gmbh Laundry detergents and laundry treatment compositions comprising dye-transfer-inhibiting dye fixatives
US20030053980A1 (en) * 2001-04-30 2003-03-20 The Gillette Company Shaving compositions containing highly lubricious water soluble polymers
US20040139559A1 (en) * 2001-05-18 2004-07-22 Juergen Detering Hydrophobically modified polyethylenimines and polyvinylamines for wrinkle-resistant finishing of textiles containing cellulose
US7141077B2 (en) * 2001-05-18 2006-11-28 Basf Aktiengesellschaft Hydrophobically modified polyethylenimines and polyvinylamines for wrinkle-resistant finishing of textiles containing cellulose
US7074750B2 (en) * 2001-06-15 2006-07-11 Basf Aktiengesellschaft Treatment method, which promotes the removal of dirt, for the surfaces of textiles and non-textiles
US20030109400A1 (en) * 2001-10-26 2003-06-12 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Care booster composition for supplementing the performance of laundry compositions
US6894017B2 (en) * 2001-11-01 2005-05-17 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Liquid detergent compositions
US20040220063A1 (en) * 2002-02-20 2004-11-04 Chappell Michael Jahi Personal cleansing compositions
US20050166333A1 (en) * 2002-04-09 2005-08-04 The Clorox Company Fabric treatment for stain release
US20050153865A1 (en) * 2002-04-09 2005-07-14 Detering Juergen Cationically modified, anionic polyurethane dispersions
US20030192130A1 (en) * 2002-04-09 2003-10-16 Kaaret Thomas Walter Fabric treatment for stain release
US20040033924A1 (en) * 2002-08-14 2004-02-19 Murphy Dennis Stephen Methods for conferring fabric care benefits during laundering
US20050097678A1 (en) * 2002-09-09 2005-05-12 Cedric Geffroy Polymer-based formulation for textile rinsing
US20050028293A1 (en) * 2002-09-09 2005-02-10 Cedric Geffroy Rinsing formulation for textiles
US20040063597A1 (en) * 2002-09-27 2004-04-01 Adair Matha J. Fabric care compositions
US20040071746A1 (en) * 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals
US20040071742A1 (en) * 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals
US20040092425A1 (en) * 2002-11-04 2004-05-13 The Procter & Gamble Company Liquid laundry detergent
US20060287216A1 (en) * 2002-12-23 2006-12-21 Zhiqiang Song Hydrophobically Modified Polymers as Laundry Additives
US20040186030A1 (en) * 2003-01-27 2004-09-23 The Procter & Gamble Company Personal cleansing composition containing irregularly shaped particles and spherical particles
US20040152616A1 (en) * 2003-02-03 2004-08-05 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Laundry cleansing and conditioning compositions
US6949498B2 (en) * 2003-02-03 2005-09-27 Unilever Home & Personal Care Usa A Division Of Conopco, Inc. Laundry cleansing and conditioning compositions
US20080160093A1 (en) * 2003-03-18 2008-07-03 James Robert Schwartz Composition comprising particulate zinc materials having a defined crystallite size
US20100307523A1 (en) * 2003-05-01 2010-12-09 Karl Shiqing Wei Striped liquid personal cleansing compositions containing a cleansing phase and a separate benefit phase comprising a high internal phase emulsion
US20050153852A1 (en) * 2003-11-04 2005-07-14 Evans Erica L. Personal cleaning compositions
US20050101505A1 (en) * 2003-11-06 2005-05-12 Daniel Wood Liquid laundry detergent composition having improved color-care properties
US7012054B2 (en) * 2003-12-03 2006-03-14 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Softening laundry detergent
US20050158489A1 (en) * 2003-12-17 2005-07-21 Fuji Photo Film Co., Ltd. Ink-jet recording medium and process for producing the same
US20050159330A1 (en) * 2004-01-16 2005-07-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent composition
US20070277327A1 (en) * 2004-04-08 2007-12-06 Clariant Produkte (Deutschland) Gmbh Detergent And Cleaning Agents Containing Dye Fixatives And Soil Release Polymers
US7304026B2 (en) * 2004-04-15 2007-12-04 Colgate-Palmolive Company Fabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient
US20060003913A1 (en) * 2004-06-30 2006-01-05 The Procter & Gamble Company Perfumed liquid laundry detergent compositions with functionalized silicone fabric care agents
US20060021150A1 (en) * 2004-07-27 2006-02-02 Cheng Hu Durable treatment for fabrics
US20060030513A1 (en) * 2004-08-03 2006-02-09 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Softening laundry detergent
US20060029625A1 (en) * 2004-08-06 2006-02-09 Niebauer Michael F Personal cleansing composition containing fibers
US20080103080A1 (en) * 2004-09-10 2008-05-01 Frank-Peter Lang Liquid Washing Agent Containing a Color Fixing Agent
US20060074005A1 (en) * 2004-10-05 2006-04-06 Ditmar Kischkel Liquid surfactant mixtures
US20060079422A1 (en) * 2004-10-08 2006-04-13 Sanjeev Midha Personal care composition containing a cleansing phase and a benefit phase
US20060083761A1 (en) * 2004-10-15 2006-04-20 The Procter & Gamble Company Personal care compositions comprising visible beads, cationic polymer, and surfactant
US20080096788A1 (en) * 2004-10-20 2008-04-24 Frank-Peter Lang Liquid Detergent Comprising Anionic Surfactants and Colour Fixing Agent
US20090048137A1 (en) * 2004-10-20 2009-02-19 Frank-Peter Lang Liquid detergent comprising secondary alkyl sulphonates and colour fixing agent
US20070190009A1 (en) * 2004-10-22 2007-08-16 Shiseido Co., Ltd. Hair Cosmetic Composition
US20080103081A1 (en) * 2004-10-23 2008-05-01 Clariant Produkte (Deutschland) Gmbh Brueningstrasse 50 Liquid Detergents Containing Colour Fixing Agents
US20080131390A1 (en) * 2004-11-09 2008-06-05 Frank-Peter Lang Hair Treatment Product Containing Anionic Surfactants and Cationic Polymers
US20060154836A1 (en) * 2005-01-12 2006-07-13 Amcol International Corporation Detersive compositions containing hydrophobic benefit agents pre-emulsified using sub-micrometer-sized insoluble cationic particles
US20060183662A1 (en) * 2005-02-16 2006-08-17 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid cleansing composition with unique sensory properties
US20070060489A1 (en) * 2005-02-17 2007-03-15 Sun James Z Cationic surfactant shampoo composition
US20060217288A1 (en) * 2005-02-17 2006-09-28 Wahl Errol H Fabric care composition
US20060199756A1 (en) * 2005-03-04 2006-09-07 Creamer Marianne P Laundry compositions and their use
US20090297463A1 (en) * 2005-04-29 2009-12-03 Andrei Serveevich Bureiko Micelle Thickening Systems for Hair Colourant and Bleaching Compositions
US20060276370A1 (en) * 2005-06-03 2006-12-07 The Procter & Gamble Company Fabric care compositions
US20070077221A1 (en) * 2005-06-23 2007-04-05 Aline Seigneurin Cosmetic composition comprising an ampholytic copolymer and another agent
US20070027050A1 (en) * 2005-07-27 2007-02-01 Conopco, Inc., D/B/A Unilever Liquid cleansing composition
US20100105592A1 (en) * 2005-08-04 2010-04-29 Mitsubishi Chemical Corporation Copolymer and detergent compositions containing the same
US20070292380A1 (en) * 2006-06-16 2007-12-20 James Anthony Staudigel Hair conditioning composition containing a non-guar galactomannan polymer derivative
US20080234165A1 (en) * 2007-03-20 2008-09-25 Rajan Keshav Panandiker Liquid laundry detergent compositions comprising performance boosters
US20090036339A1 (en) * 2007-03-30 2009-02-05 Anne Sans Mild, foaming cleansing composition
US20080261845A1 (en) * 2007-04-20 2008-10-23 Kao Corporation Skin cleansing compositions
US20100310644A1 (en) * 2007-12-21 2010-12-09 BASF ,Trademarks and Licenses Anti-dandruff compositions containing peptides

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100144579A1 (en) * 2007-08-08 2010-06-10 Volkel Theodor Color-Safe Detergent or Cleaning Agent having Optical Brightener
US20140352076A1 (en) * 2013-05-31 2014-12-04 Haiyan Song Laundry detergents
WO2016200440A1 (en) 2015-06-11 2016-12-15 The Procter & Gamble Company Device and methods for applying compositions to surfaces
US20170166843A1 (en) * 2015-12-10 2017-06-15 The Procter & Gamble Company Process of making a liquid laundry detergent composition
US20190048296A1 (en) * 2017-08-10 2019-02-14 Henkel IP & Holding GmbH Unit dose detergent products with improved pac rigidity
US10927324B1 (en) * 2019-08-28 2021-02-23 Henkel IP & Holding GmbH Unit-dose detergent compositions containing polyethylene glycol and an organic acid

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